CN103113862B - Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid - Google Patents
Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid Download PDFInfo
- Publication number
- CN103113862B CN103113862B CN201310072072.2A CN201310072072A CN103113862B CN 103113862 B CN103113862 B CN 103113862B CN 201310072072 A CN201310072072 A CN 201310072072A CN 103113862 B CN103113862 B CN 103113862B
- Authority
- CN
- China
- Prior art keywords
- temperature
- agent
- high temperature
- ultra
- drilling fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an amphoteric ionic ultra-high-temperature polysulfonate drilling fluid. The amphoteric ionic ultra-high-temperature polysulfonate drilling fluid comprises the components in percentage by mass as follows: 4.0-6.0% of bentonite, 0.5-0.8% of an amphoteric ionic polymer coating agent, 0.8-1.2% of an amphoteric ionic polymer diluting agent, 3-4% of a filtrate reducer resistant to high temperature, 3-4% of a compound filtrate reducer resistant to high temperature, 2-3% of a high temperature stabilizer, 0.2-0.3% of caustic soda, 3-4% of an inert blocking agent and the balance of water, wherein the amphoteric ionic polymer coating agent is prepared by using acrylamide, acrylic acid, sodium allyl sulfonate and dimethyl diallyl ammonium chloride as raw materials and using N1,N1,N2,N2-tetra-allyl ethylene diamine as a cross-linking agent; and the amphoteric ionic polymer diluting agent is prepared by using acrylamide, sodium allyl sulfonate and dimethyl diallyl ammonium chloride as raw materials. The amphoteric ionic ultra-high-temperature polysulfonate drilling fluid has the characteristics that the amphoteric ionic polymer and the ultra-high-temperature stabilizer are introduced into the polysulfonate drilling fluid system to enhance the high-temperature resistance of the water-based polysulfonate drilling fluid.
Description
Art
The present invention relates to the high temperature resistance sulphonated polymer mud system in the drilling engineering of petroleum natural gas exploration field, by introducing amphoteric ion polymer and high temperature protection agent in sulphonated polymer mud system, this system high-temperature resistance being promoted to 250 DEG C.
Background technology
Along with shallow-layer, the exhaustion of mid-deep strata hydrocarbon resources amount and the growing of Demand of Oil & Gas amount, oil-gas exploration becomes inexorable trend to deep layer, the extension of ultra-deep layer field.But deep oil-gas reservoir probing exploitation is faced with the critical conditions of high temperature ultrahigh-temperature, has higher requirement to drilling fluid high-temperature resistance.Conventional water-base drilling fluid temperature resistance scarce capacity becomes a large obstacle of restriction ultra deep well, the drilling well of superelevation hot-well.Improve water-base drilling fluid high-temperature resistance and become one of gordian technique of superelevation hot-well probing.The composition research of superhigh temperature water base drilling fluid and temperature resistance merit rating are the scientific basics implementing superhigh temperature water base drilling fluid technical scheme.
What current China ultra deep well, superelevation hot-well adopted is mostly poly-sulphur water base drilling fluid system, this system treatment agent formation comprises polymeric main polymers, thinner, sulfonation class fluid loss agent, main polymers mostly is anionic high molecular polymer, thinner is anionic molecular weight polymers, its molecular chain comprises adsorption group and the large functional groups of aquation group two.Adsorption group mostly is-OH ,-CN ,-CONH
2, its mechanism of action is that adsorption group is surperficial at bentonite clay particle by adsorption by hydrogen bond, aquation group (-COO
-,-CH
2sO
3 -) aquation is that planar water film is brought on bentonite clay particle surface, stops the gathering of clay particle, the colloidal dispersions state of protection bentonite clay particle, thus stable property of drilling fluid is provided.Because the adsorption strength of hydrogen bond is not high enough, the attached trend of desorption under high temperature is comparatively strong, and therefore handled sulphonated polymer mud high-temperature resistance is generally limited to less than 200 DEG C.Temperature is more than 200 DEG C, and often occur that drilling fluid high-temperature high pressure dehydration is significantly risen, rheological worsens after high temperature, show as high temperature gelling or high temperature coagulation, severe patient drilling fluid loses colloid property, and performance is destroyed, and structure is disintegrated.
Ultra-high temperature drilling liquid is the important technology guarantee of superelevation hot-well drilling well, traditional poly-sulphur water-base drilling fluid temperature resistance ability is below 200 DEG C, be difficult to the probing needs of satisfied increasing ultra deep well, superelevation hot-well, the novel poly-sulphur water-base drilling fluid tool that research and development possess anti-ultrahigh-temperature ability is of great significance.
Summary of the invention
Zwitter-ion is the object of the present invention is to provide to gather sulphur ultra-high temperature drilling liquid, by introducing amphoteric ion polymer and ultrahigh-temperature stablizer in sulphonated polymer mud system, this system high-temperature resistance is promoted to 250 DEG C, greatly improve the high-temperature resistance of poly-sulphur water-base drilling fluid, overcome defect and the deficiency of prior art.
In order to reach above-mentioned technical purpose, the invention provides following technical scheme.
Zwitter-ion gathers sulphur ultra-high temperature drilling liquid, is made up of in mass ratio following component:
Wilkinite 4.0 ~ 6.0 quality %,
Amphoteric ion polymer coating agent 0.5 ~ 0.8 quality %,
Amphoteric ion polymer thinner 0.8 ~ 1.2 quality %,
Heat resisting fluid loss reducing agent 3 ~ 4 quality %,
High temperature resistance compound fluid loss agent 3 ~ 4 quality %,
High-temperature stabiliser 2 ~ 3 quality %,
Caustic soda 0.2 ~ 0.3 quality %,
Inertia plugging agent 3 ~ 4 quality %,
All the other are water.
In the present invention, described amphoteric ion polymer coating agent is cross-linking copolymer, with acrylamide, vinylformic acid, sodium allylsulfonate, dimethyl diallyl ammonium chloride for raw material, with N
1, N
1, N
2, N
2-tetraallylethylene diamine is that linking agent is prepared from, and molecular weight is about 2,000,000.
Described amphoteric ion polymer thinner is the small molecular weight polymer prepared for raw material with acrylamide, sodium allylsulfonate and dimethyl diallyl ammonium chloride, and molecular weight is about 2000, commercially available, product designation XY-27.
Described heat resisting fluid loss reducing agent is sulfomethylation resol, is called for short sulfonated phenol formaldehyde resin.
Described high temperature resistance compound fluid loss agent is sulfomethylation humic acids, is called for short sulfonated lignite resin.
Described high-temperature stabiliser is aluminum chloride complexing sulfomethylation humic acids, is the complex compound that aluminium salt and sulfomethylation humic acids generate.
Described inertia plugging agent is calcium carbonate superfine powder, calcium carbonate powder particle diameter 2 μm of < d≤5 μm.
Above-mentioned substance, except zwitter-ion coating agent, is commercially available.
In the present invention, take montmorillonite as the wilkinite of main mineral constituent, there is hydrability, swelling property and dispersiveness.Be separated into the colloidal solid of < 2 μm at drilling fluid system camber, fine and close mud cake can be formed at infiltrative surface of stratum, stabilizing borehole and prevention solid phase, the further invaded formation of liquid phase.In addition; bentonite colloidal particle also can with high molecular polymer by adsorbing, building bridge forms space net structure; the rheological characteristicss such as the viscosity needed for drilling fluid, shear force, thixotropy, shear thinning behavior are provided, realize that drilling fluid carries, the function of suspend landwaste and high-density weighting material.
Caustic soda gathers in sulphur ultra-high temperature drilling liquid at zwitter-ion mainly provides OH
-, improve the pH value of drilling fluid, slow down high temperature passivation and the high temperature aggregation tendency of bentonite clay particle, strengthen the stress efficacy of high temperature resistance compound fluid loss agent.
Amphoteric ion polymer coating agent is with N
1, N
1, N
2, N
2-tetraallylethylene diamine is linking agent, and with acrylamide, vinylformic acid, sodium allylsulfonate and dimethyl diallyl ammonium chloride for monomer, quarternary copolymerized crosslinked new polymers coating agent, molecular weight is about 2,000,000.Both containing-COO on its molecular chain
-,-SO
3 -the strong aquation group of negatively charged ion, also containing cation group, and cation group and the positive electronegativity of electronegative clay particle are adsorbed, greatly strengthen adsorption strength, a small amount of cation group just can provide the effect because a large amount of non-ionic group is obtained by adsorption by hydrogen bond, thus can discharge more space and make way for anionic group on molecular chain.More, stronger anionic group aquation, for clay particle wears thicker, finer and close absorption hydration shell, makes the colloidal property of clay particle more stable.Therefore the adsorptive power of amphoteric ion polymer coating agent and hydratability are better than traditional anionic polymer coating agent, and can overcome the desorption under hot conditions, go hydration effect, therefore high-temperature resistance is stronger.
Amphoteric ion polymer thinner is by a kind of small molecular weight polymer of acrylamide, sodium allylsulfonate and dimethyl diallyl ammonium chloride multi-component copolymer, molecular weight is about 2000, on molecular chain except the anionic group of larger proportion, non-ionic group, also containing cation group.Organic cationic groups can in the faster more firm absorption of electronegative clay particle surface, Some substitute or broken amphoteric ion polymer coating agent and clay particle adsorbs the space grid structure formed, and reaches the effect of dilution.The electrical adsorption strength of this organic cationic groups and clay particle, therefore can the impact of anti-ultrahigh-temperature much larger than adsorption by hydrogen bond intensity.On the other hand; be adsorbed on direct that hydration shell that anionic groups a large amount of on the diluent molecule chain of clay particle surface and non-ionic group aquation bring and solvated layer prevent between clay particle to contact; especially there is the sulfonate groups of strong hydratability; even if still there is good hydratability under ultra-high temperature condition; for clay particle provides enough aquation protective membranes; therefore under ultra-high temperature condition, the appropriateness of clay particle still can be kept to disperse, improve the coagulation stability of drilling fluid system.
Heat resisting fluid loss reducing agent is sulfonated phenol formaldehyde resin and modifier thereof, and molecular weight is about 10000.Containing a large amount of-OH in the molecular structure of sulfonated phenol formaldehyde resin, can in clay particle surface by hydrogen bond generation multipoint adsorption ,-the CH on molecular chain
2sO
3 -it is a kind of superpower hydrophilic radical; thicker hydration shell and solvated layer can be formed; effectively can resist the impact of high temperature dehydration; even if still available protecting can be provided for clay particle under ultrahigh-temperature; stop the coalescent of clay particle; keep dispersion state and the colloid property of clay particle, be conducive to forming fine and close mud cake.In addition the formation of sulphur methyl aquation has higher viscoelastic adsorption solvent layer also good plug-hole effect, greatly reduces drilling fluid dehydration.
In ultra-high temperature drilling liquid system, single high temperature fluid loss agent is difficult to control High Temperature High Pressure dehydration < 20ml/30min, the present invention is also composite another kind of heat resisting fluid loss reducing agent sulfonated lignite resin except sulfonated phenol formaldehyde resin, be brown coal and formaldehyde, S-WAT in the basic conditions sulfomethylation form.Filtrate reducing mechanism and sulfonated phenol formaldehyde resin similar, be all utilize strong adsorption group to be adsorbed on clay particle surface, under ultra-high temperature condition, be still in strong aquation group-CH
2sO
3 -the protection of thicker hydration shell under, keep the dispersion state of clay particle, form fine and close mud cake, reduce filter loss.In addition, sulfonated lignite resin and sulfonated phenol formaldehyde resin all can with high volence metal ion complexing, make treatment agent and clay form stronger positive electro-adsorption, reduce the trend that treatment agent desorption under high temperature is attached, improve the high-temperature resistance for the treatment of agent.
High-temperature stabiliser in the present invention adopts by sulfomethylation humic acids and high volence metal ion Al
3+the product of crosslinking reaction.Its Main Function is the high temperature rheology energy of stable drilling fluid, avoids drilling fluids at high temperature dilution, high temperature multiviscosisty, high temperature gelling or high temperature coagulation.The hydroxybenzene mixture of carboxylic acids that humic acids is a kind of complexity, molecular weight is uneven, structure is different.There is a large amount of adsorption group in molecular structure as phenolic hydroxyl group, alcoholic extract hydroxyl group, also have a large amount of strong aquation group-COONa, have stronger adsorptive power and hydratability in clay particle surface.After introducing metal ion by complex reaction, the high-temperature stabiliser adsorptive power obtained and hydratability strengthen further, effectively can solve the instability problem of drilling fluid rheological property under ultrahigh-temperature.The effect of high volence metal ion has following 3 points.1. with the sulfonated phenol formaldehyde resin in poly-sulphur system, sulfonated lignite resin formation complex compound, and at high temperature appropriately crosslinked, molecular weight appropriateness increases, and offsets the impact for the treatment of agent high temperature degradation, stablize drilling fluids at high temperature rheological, avoid drilling fluids at high temperature to dilute or solid phase high temperature coagulation in drilling fluid.2. suppress clay particle High Temperature Disperse, avoid drilling fluids at high temperature multiviscosisty or high temperature gelling.3. the electrical absorption of enhancement process agent and clay particle, reduces the attached trend for the treatment of agent desorption under high temperature, and the colloidal property of protection clay particle, controls the high temperature dehydration performance of sulphonated polymer mud.
The main component of inertia plugging agent is calcium carbonate, calcium carbonate powder particle diameter 2 μm of < d≤5 μm.Its Main Function is for increasing solid phase particles concentration in drilling fluid, make up the deficiency of solid phase particles in ultra-high temperature drilling liquid, form mud cake together with bentonite clay particle, improvement of mud cake, reduce mud cake rate of permeation, thus reach the effect reducing drilling fluid high-temperature high pressure dehydration.Because it does not substantially affect other performance of drilling fluid in inertia in drilling fluid.
To sum up, the present invention is in poly-sulphur water-base drilling fluid, anionic polymer is replaced with amphoteric ion polymer, utilize the electrical absorption of the cation group on amphoteric ion polymer molecular chain and electronegative clay particle surface, strengthen the adsorption strength of polymer treatment agent and clay particle, reduce the trend that treatment agent desorption under high temperature is attached, greatly promote the high-temperature resistance of sulphonated polymer mud.Introduce high-temperature stabiliser simultaneously, the crosslinking effect utilizing high volence metal ion and treatment agent, the High Temperature Disperse effect suppressing clay particle and the electrical adsorption with clay particle, greatly improve the adsorption strength for the treatment of agent in clay particle surface, stop the coalescent and High Temperature Disperse of the high temperature of clay particle, keep the appropriate dispersion state of clay particle, improve the high temperature dehydration performance of sulphonated polymer mud, stablize the high temperature rheology energy of sulphonated polymer mud.
The structure of amphoteric ion polymer coating agent of the present invention is as follows:
X, y, m, n are respectively dimethyl diallyl ammonium chloride, acrylamide, sodium allylsulfonate, acrylic acid structural unit percentage ratio, i.e. molecular fraction.X is 8 ~ 10%, y be 25 ~ 30%, m is 20 ~ 30%, n=1-x-y-m.
This zwitter-ion coating agent by acrylamide, vinylformic acid, sodium allylsulfonate, dimethyl diallyl ammonium chloride, N
1, N
1, N
2, N
2-tetraallylethylene diamine is raw material preparation.
The preparation process of amphoteric ion polymer coating agent is as follows:
(1) linking agent N
1, N
1, N
2, N
2the preparation of-tetraallylethylene diamine:
Under ice bath, instilled by propenal in the methanol solution of quadrol, the mol ratio of propenal and quadrol is 2:1, and the mass ratio of quadrol and methyl alcohol is 1:2, and reaction 30min, 50 DEG C of vacuum-dryings, obtain N
1, N
2-diallyl imines quadrol, productive rate 80%; By N
1, N
2-diallyl imines quadrol is dissolved in ethanol, drips the ethanolic soln of sodium borohydride, N
1, N
2-diallyl imines quadrol and sodium borohydride mol ratio 1:1.2, the mass ratio of sodium borohydride and ethanol is 1:2, and room temperature reaction 3h, obtains N
1, N
2-diallyl quadrol, by the propenyl chloride of twice molar weight instillation N under ice bath
1, N
2-diallyl quadrol, drips off rear control temperature of reaction 70 DEG C, continues reaction 3h, obtains linking agent N
1, N
1, N
2, N
2-tetraallylethylene diamine.
Its reaction scheme is as follows:
(2) preparation of zwitter-ion coating agent:
Acrylamide, vinylformic acid, sodium allylsulfonate, dimethyl diallyl ammonium chloride are configured to the aqueous solution of 25% with mol ratio 3:3:3:1, azo diisobutyl miaow hydrochloride is initiator, and its consumption is 0.5%, linking agent N of total monomer mass
1, N
1, N
2, N
2the consumption of-tetraallylethylene diamine is 0.05% of total monomer mass, reacts 3h, obtain amphoteric ion polymer coating agent at 45 DEG C.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of zwitter-ion coating agent
Embodiment
One, the spectrum analysis of zwitter-ion coating agent
See Fig. 1.3434.60cm
-1belong to OH stretching vibration, 3197.40cm
-1belong to the stretching vibration of N-H, 2935.13cm
-1and 2863.77cm
-1belong to methylene radical C-H stretching vibration, 1670.05cm
-1belong to carbonylic stretching vibration, 1625.70cm
-1belong to the stretching vibration of amidocarbonylation, 1450.20cm
-1belong to the in-plane bending vibration of C-H, 1400.07cm
-1belong to the stretching vibration of gem-dimethyl, 1174.44cm
-1and 1122.37cm
-1belong to the stretching vibration of sulfonic acid, 850.45cm
-1belong to O-H out-of-plane deformation vibration.The synthesizing cross-linked tetrapolymer of merit is may be described as by infrared spectra.
Two, zwitter-ion gathers the preparation of sulphur ultra-high temperature drilling liquid
The preparation of bentonite base slurry: measure tap water 500ml, pour in 1000ml Enamel jar, is placed on stirring at low speed under stirrer, takes 20 grams ~ 30 grams wilkinites (4% ~ 6%) and be slowly added to the water.Wilkinite adds rear continuation stirring at low speed 20 minutes, stops stirring, and is poured into by bentonite slurry in high-speed stirring cup, stirs 2 minutes (11000 revs/min) with homogenizer, then leaves standstill aquation 24 hours.
Zwitter-ion gathers the preparation of sulphur ultra-high temperature drilling liquid: be placed on low-speed mixer by the prehydration bentonite base of 24 hours slurry, (1500 revs/min) slowly add amphoteric ion polymer coating agent successively under agitation, amphoteric ion polymer thinner, heat resisting fluid loss reducing agent, high temperature resistance compound fluid loss agent, high-temperature stabiliser, caustic soda, inertia plugging agent, adding rear continuation stirring was placed on electromagnetic oven after 10 minutes, be heated to 65 DEG C under agitation, then under this drilling fluid being placed in homogenizer, (11000 revs/min) stir 2 minutes, stir (600 revs/min) to temperature under being again placed on low-speed mixer and drop to 45 DEG C.Then the performance such as rheological parameter, density, middle pressure dehydration API, pH, High Temperature High Pressure dehydration HTHP is measured.Example 1, example 2 all complete by aforesaid operations, and its per-cent is mass percent.
Example 1
Example 2
Three, zwitter-ion gathers the performance test of sulphur ultra-high temperature drilling liquid
(1) zwitter-ion gathers the heat rolling front and back performance comparison of sulphur ultra-high temperature drilling liquid
Performance measurement before high temperature: measure the performance of drilling fluid, comprises rheological parameter (as apparent viscosity (mPas), plastic viscosity (mPas), yield value (Pa)), density (g/cm
3), middle pressure dehydration API(ml), High Temperature High Pressure dehydration HTHP(ml) etc.
High temperature rolls: drilling fluid is loaded high temperature ageing tank and put into roller furnace, (general 220 ~ 260 DEG C of the high temperature according to reality is born) heat is rolled 16 hours at a set temperature, water-bath is opened high temperature ageing tank and is poured out drilling fluid after being cooled to 60 DEG C, under low-speed mixer stirs, be cooled to 45 DEG C.
Performance measurement after high temperature rolls: the property of drilling fluid being cooled to 45 DEG C after rolling to high temperature measures, and comprises rheological parameter (apparent viscosity (mPas), plastic viscosity (mPas), yield value (Pa)), density, middle pressure dehydration API(ml), High Temperature High Pressure dehydration HTHP(ml), High Temperature High Pressure rheological parameter.
Defining of anti-ultrahigh-temperature (250 DEG C) ability: (1) heat rolling forward and backward High Temperature High Pressure dehydration (250 DEG C) < 20ml/30min; (2) after heat rolling, (250 DEG C) rheological parameter is basicly stable, can not occur serious dilution, significantly thickening, solid phase coagulation or high-temp glue coagulation phenomena; (3) High Temperature High Pressure (250 DEG C, 60MPa) rheological parameter is reasonable, and namely apparent viscosity, plastic viscosity are low as far as possible, but yield value need remain on 5 ~ 10MPa scope.
Performance comparison before and after the rolling of table 1 heat
Note: hot rolling temperature is 250 DEG C, 16 hours time, High Temperature High Pressure dehydration HTHP is 250 DEG C.
The experimental data of example 1, example 2 from table 1, before and after 250 DEG C of high temperature roll, rheological parameter is basicly stable, and apparent viscosity, plastic viscosity slightly increase, and example 1 yield value remains unchanged.Example 2 because of high-temperature stabiliser dosage less, yield value declines to some extent, but does not all occur that the drilling fluids such as serious dilution, significantly thickening, coagulation, gelling can worsen or the phenomenon such as structure disintegration.And before and after high temperature rolling, 250 DEG C of High Temperature High Pressure dehydrations are slightly risen, but the standard of equal < 20ml/30min.Show that zwitter-ion gathers the ability that sulphur ultra-high temperature drilling liquid system possesses anti-250 DEG C of high temperature.
(2) high-temperature stable agent content gathers the performance impact of sulphur ultra-high temperature drilling liquid to zwitter-ion
In order to the effect of high-temperature stabiliser is better described, when other material proportionings are constant, only change the consumption (see table 2) of high-temperature stabiliser, after rolling, test mud property.
Table 2 high-temperature stable agent content gathers the performance impact of sulphur ultra-high temperature drilling liquid to zwitter-ion
Note: hot rolling temperature is 220 DEG C, 16 hours time.
As can be seen from Table 2, do not increasing temperature in stablizer situation, after 220 DEG C of heat are rolled, drilling fluid yield value is reduced to the lower numerical value of 1.5Pa, when high-temperature stabiliser dosage is 1%, after 220 DEG C of heat are rolled, yield value value reaches 6.3Pa, along with high-temperature stabiliser dosage increases, yield value is in progressively ascendant trend.Show that high-temperature stabiliser has yield value after stable high temperature to act on very significantly.
(3) amphoteric ion polymer coating agent content gathers the performance impact of sulphur ultra-high temperature drilling liquid to zwitter-ion
In the present invention, amphoteric ion polymer coating agent adopts novel cross-linked polymer, molecular weight about 2,000,000, and its stability is better than traditional direct linkage type amphoteric ion polymer and anionic polymer, can overcome the desorption under hot conditions, go hydration effect, therefore high-temperature resistance is stronger.In order to the effect of crosslinked amphoteric ion polymer coating agent is described, when other components are constant, change the consumption (see table 3) of crosslinked amphoteric ion polymer coating agent, configure mud and test performance.
Table 3 amphoteric ion polymer coating agent content gathers the performance impact of sulphur ultra-high temperature drilling liquid to zwitter-ion
Note: hot rolling temperature is 220 DEG C, 16 hours time, High Temperature High Pressure dehydration HTHP is 220 DEG C.
As can be seen from Table 3, do not adding in amphoteric ion polymer coating agent situation, after 220 DEG C of heat are rolled, 220 DEG C of High Temperature High Pressure dehydrations are up to 32ml/30min, and apparent viscosity is 15.5mPas only, and after adding 0.5% amphoteric ion polymer coating agent, 220 DEG C of High Temperature High Pressure dehydrations are reduced to 19ml/30min, and apparent viscosity brings up to 21.8mPas, and along with the increase of amphoteric ion polymer coating agent consumption, 220 DEG C of High Temperature High Pressure dehydrations progressively reduce, and apparent viscosity enlarges markedly.Show in drilling fluid system, amphoteric ion polymer coating agent has the effect of raising system high-temperature resistance, shows as thickening under ultra-high temperature condition and controls the effect of High Temperature High Pressure dehydration.
(4) zwitter-ion gathers the High Temperature High Pressure rheological parameter test of sulphur ultra-high temperature drilling liquid
The High Temperature High Pressure rheological parameter test of table 4 example 1 drilling fluid
The High Temperature High Pressure rheological parameter test of table 5 example 2 drilling fluid
As can be seen from table 4, table 5, zwitter-ion of the present invention gathers sulphur ultra-high temperature drilling liquid within the scope of 230 ~ 250 DEG C of ultrahigh-temperature, and rheological parameter is excellent, be embodied in apparent viscosity, plastic viscosity declines to a great extent, and yield value remains on the zone of reasonableness of 8 ~ 10MPa.And after cooling to normal temperature, drilling fluid rheology recovers substantially, there is not gelling or coagulation phenomenon after high temperature.Further proof zwitter-ion sulphonated polymer mud has the ability of anti-250 DEG C of ultrahigh-temperature.
(5) contrast experiment of traditional sulphonated polymer mud and zwitter-ion sulphonated polymer mud temperature resistance ability of the present invention
Experiment condition is identical, and in traditional sulphonated polymer mud, main polymers is anionic superpolymer, and in zwitter-ion sulphonated polymer mud, main polymers is amphoteric ion type superpolymer.Except main polymers, other composition is identical.
The sulphonated polymer mud that table 6 is traditional and zwitter-ion sulphonated polymer mud component table (being mass percent)
The sulphonated polymer mud that table 7 is traditional and zwitter-ion sulphonated polymer mud performance comparison
Note: experimental temperature is 220 DEG C.
As can be seen from Table 7, traditional sulphonated polymer mud rheological parameter is very low, and 220 DEG C of High Temperature High Pressure dehydration HTHP are up to 56ml, and the rheological parameter such as apparent viscosity, yield value is extremely low, show that this system can not resist the high temperature of 220 DEG C.And the 220 DEG C of High Temperature High Pressure dehydrations of zwitter-ion sulphonated polymer mud are 18ml, the rheological parameters such as apparent viscosity, plastic viscosity, yield value are in zone of reasonableness, show that this system can bear the high temperature of 220 DEG C.Show zwitter-ion sulphonated polymer mud has better thermostability and Geng Gao temperature resistance ability relative to negatively charged ion sulphonated polymer mud.
Claims (2)
1. zwitter-ion gathers sulphur ultra-high temperature drilling liquid, is made up of in mass ratio following component:
Wilkinite 4.0 ~ 6.0 quality %,
Amphoteric ion polymer coating agent 0.5 ~ 0.8 quality %,
Amphoteric ion polymer thinner 0.8 ~ 1.2 quality %,
Heat resisting fluid loss reducing agent 3 ~ 4 quality %,
High temperature resistance compound fluid loss agent 3 ~ 4 quality %,
High-temperature stabiliser 2 ~ 3 quality %,
Caustic soda 0.2 ~ 0.3 quality %,
Inertia plugging agent 3 ~ 4 quality %,
All the other are water;
Described amphoteric ion polymer coating agent is cross-linking copolymer, with acrylamide, vinylformic acid, sodium allylsulfonate, dimethyl diallyl ammonium chloride for raw material, with N
1, N
1, N
2, N
2-tetraallylethylene diamine is that linking agent is prepared from, molecular weight 2,000,000;
Described amphoteric ion polymer thinner is the small molecular weight polymer prepared for raw material with acrylamide, sodium allylsulfonate and dimethyl diallyl ammonium chloride, molecular weight 2000;
Described heat resisting fluid loss reducing agent is sulfomethylation resol;
Described high temperature resistance compound fluid loss agent is sulfomethylation humic acids;
Described high-temperature stabiliser is aluminum chloride complexing sulfomethylation humic acids;
Described inertia plugging agent is calcium carbonate superfine powder, calcium carbonate powder particle diameter 2 μm of < d≤5 μm.
2. zwitter-ion as claimed in claim 1 gathers sulphur ultra-high temperature drilling liquid, and it is characterized in that, described amphoteric ion polymer coating agent is prepared by the following method:
(1) linking agent N
1, N
1, N
2, N
2the preparation of-tetraallylethylene diamine: under ice bath, instills propenal in the methanol solution of quadrol, and the mol ratio of propenal and quadrol is 2:1, and the mass ratio of quadrol and methyl alcohol is 1:2, and reaction 30min, 50 DEG C of vacuum-dryings, obtain N
1, N
2-diallyl imines quadrol, by N
1, N
2-diallyl imines quadrol is dissolved in ethanol, drips the ethanolic soln of sodium borohydride, N
1, N
2the mol ratio of-diallyl imines quadrol and sodium borohydride is 1:1.2, and the mass ratio of sodium borohydride and ethanol is 1:2, and room temperature reaction 3h, obtains N
1, N
2-diallyl quadrol, by the propenyl chloride of twice molar weight instillation N under ice bath
1, N
2-diallyl quadrol, controls temperature of reaction 70 DEG C, and reaction 3h, obtains linking agent N
1, N
1, N
2, N
2-tetraallylethylene diamine;
(2) preparation of amphoteric ion polymer coating agent: acrylamide, vinylformic acid, sodium allylsulfonate, dimethyl diallyl ammonium chloride are configured to the aqueous solution of 25% with mol ratio 3:3:3:1, azo diisobutyl miaow hydrochloride is initiator, its consumption is 0.5%, linking agent N of total monomer mass
1, N
1, N
2, N
2the consumption of-tetraallylethylene diamine is 0.05% of total monomer mass, reacts 3h, obtain amphoteric ion polymer coating agent at 45 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310072072.2A CN103113862B (en) | 2013-03-07 | 2013-03-07 | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310072072.2A CN103113862B (en) | 2013-03-07 | 2013-03-07 | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103113862A CN103113862A (en) | 2013-05-22 |
| CN103113862B true CN103113862B (en) | 2014-12-24 |
Family
ID=48412283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310072072.2A Expired - Fee Related CN103113862B (en) | 2013-03-07 | 2013-03-07 | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113862B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315974A (en) * | 2014-06-17 | 2016-02-10 | 成都棕通石油配件有限公司 | Anti-sloughing drilling fluid |
| CN107245329B (en) * | 2017-07-12 | 2018-03-20 | 西南石油大学 | Deep-well sulphonated polymer mud and preparation method thereof |
| CN108264890B (en) * | 2018-01-22 | 2019-01-01 | 中国石油大学(华东) | A kind of preparation method of micro-cross-linked water-base drilling fluid fluid loss additive |
| CN110511310B (en) * | 2019-09-04 | 2021-08-20 | 大庆华营化工有限公司 | Preparation method of coating agent for drilling fluid |
| CN113122195A (en) * | 2020-01-11 | 2021-07-16 | 中石化石油工程技术服务有限公司 | High-temperature-resistant high-density water-based drilling fluid |
| CN111334278B (en) * | 2020-04-16 | 2022-05-13 | 陕西科技大学 | Sulfonated humic acid fracturing fluid and preparation method thereof |
| CN111621271A (en) | 2020-05-11 | 2020-09-04 | 中国石油大学(北京) | Saturated saline drilling fluid of salt response type intelligent polymer and preparation method thereof |
| CN113930222B (en) * | 2021-10-15 | 2022-10-14 | 西南石油大学 | High-temperature-resistant high-density polysulfonate water-based drilling fluid and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6281172B1 (en) * | 1999-04-07 | 2001-08-28 | Akzo Nobel Nv | Quaternary nitrogen containing amphoteric water soluble polymers and their use in drilling fluids |
| CN101148579A (en) * | 2007-10-27 | 2008-03-26 | 东营泰尔石油技术有限公司 | High temperature resistant circulating micro-foam drilling fluid or completion fluid |
| CN102352223A (en) * | 2011-07-22 | 2012-02-15 | 石家庄华莱鼎盛科技有限公司 | Hydrolyzed polyacrylonitrile-bipoly ammonium salt for drilling fluid |
| CN102433107A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low-molecular-weight polymer type filtrate loss reducer for drilling fluid and preparation method for same |
| CN102477287A (en) * | 2010-12-08 | 2012-05-30 | 深圳市钻通工程机械股份有限公司 | Drilling fluid and composite additive |
-
2013
- 2013-03-07 CN CN201310072072.2A patent/CN103113862B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6281172B1 (en) * | 1999-04-07 | 2001-08-28 | Akzo Nobel Nv | Quaternary nitrogen containing amphoteric water soluble polymers and their use in drilling fluids |
| CN101148579A (en) * | 2007-10-27 | 2008-03-26 | 东营泰尔石油技术有限公司 | High temperature resistant circulating micro-foam drilling fluid or completion fluid |
| CN102433107A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low-molecular-weight polymer type filtrate loss reducer for drilling fluid and preparation method for same |
| CN102477287A (en) * | 2010-12-08 | 2012-05-30 | 深圳市钻通工程机械股份有限公司 | Drilling fluid and composite additive |
| CN102352223A (en) * | 2011-07-22 | 2012-02-15 | 石家庄华莱鼎盛科技有限公司 | Hydrolyzed polyacrylonitrile-bipoly ammonium salt for drilling fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103113862A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113862B (en) | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid | |
| CN104178102B (en) | Cross-linkable high-temperature-resistant residue-free multi-component copolymerization type fracturing fluid and preparation method thereof | |
| WO2017084379A1 (en) | Multifunctional composite fracturing fluid system | |
| US20200283673A1 (en) | Thermosensitive Self-plugging Bentonite and Preparation Method Thereof and Water-based Drilling Fluid | |
| CN102206484B (en) | Acidic water repellent associated matter fracturing fluid | |
| CN110373165B (en) | Application of amino acid modified graphene oxide as coating agent in water-based drilling fluid | |
| CN110484229B (en) | Composite oil displacement system for low-permeability oil reservoir and preparation and application methods thereof | |
| CN112159651B (en) | Multifunctional thickening agent and preparation method thereof | |
| CN110511734B (en) | Based on MoS2Method for preparing multifunctional slickwater by nanosheets | |
| CN111394073B (en) | High-temperature-resistant oil testing oil-based well completion fluid and preparation method and application thereof | |
| CN111574973A (en) | Three-water-retention-based drilling fluid system | |
| WO2019010771A1 (en) | Deep-well polysulfonate drilling fluid and preparation method therefor | |
| CN113698534A (en) | Polymer for high-performance environment-friendly borehole wall stabilizer for water-based drilling fluid | |
| CN113930222B (en) | High-temperature-resistant high-density polysulfonate water-based drilling fluid and preparation method thereof | |
| CN111218268B (en) | Slickwater for compact sandstone reservoir and preparation method thereof | |
| CN111876138B (en) | Carbon-based tackifier and preparation method and application thereof | |
| CN111205396B (en) | Graft modified xanthan gum and preparation method and application thereof | |
| CN110804428A (en) | Profile control composition, profile control agent and preparation method thereof | |
| CN110606909A (en) | Flow pattern regulator copolymer for drilling fluid and preparation method thereof | |
| CN112552886B (en) | Superhigh temperature resistant 180 ℃ variable density solid-free tackifying type well completion fluid and workover fluid | |
| CN109777394B (en) | Preparation method of self-suspending self-degrading proppant | |
| CN110387006B (en) | Acrylamide polymer inverse emulsion and application thereof as supramolecular coating agent in water-based drilling fluid | |
| CN109749009B (en) | Preparation method of anti-drag film composition | |
| CN109627378B (en) | Hydrophobic association complex and preparation method thereof, clean diverting acid for heterogeneous carbonate reservoir acid fracturing and preparation method thereof | |
| CN101942295B (en) | High temperature resisting rectorite water base drilling fluid for deep stratigraphical drilling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20160307 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |