CN105154035A - Amphoteric phenolic resin high-temperature drilling fluid filtrate reducer and preparation method thereof - Google Patents

Amphoteric phenolic resin high-temperature drilling fluid filtrate reducer and preparation method thereof Download PDF

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CN105154035A
CN105154035A CN201510575796.8A CN201510575796A CN105154035A CN 105154035 A CN105154035 A CN 105154035A CN 201510575796 A CN201510575796 A CN 201510575796A CN 105154035 A CN105154035 A CN 105154035A
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CN105154035B (en
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何毅
范毅
罗平亚
王平全
杨冉冉
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Chengdu Shida Lidun Technology Co ltd
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Southwest Petroleum University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

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Abstract

The invention discloses an amphoteric phenolic resin high-temperature drilling fluid filtrate reducer and a preparation method thereof. The preparation method comprises the following steps: (1) reacting by virtue of phenol, formaldehyde and hordenine according to a molar ratio of 10 to (10-15) to (1-2), so as to obtain cationized linear resin; (2) mixing sodium pyrosulfite with distilled water in the same mass, and dropwise adding a formaldehyde solution to react, so as to obtain a sulfomethylation agent; and (3) reacting by virtue of phenol, the sulfomethylation agent, the formaldehyde solution and the cationized linear resin, dropwise adding an iodomethane solution in a dark condition, so as to obtain the amphoteric phenolic resin high-temperature drilling fluid filtrate reducer. The preparation method is simple and is high in yield and low in cost, and the prepared amphoteric phenolic resin high-temperature drilling fluid filtrate reducer has relatively high temperature resistance and salt resistance at low usage.

Description

A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent and preparation method thereof
Technical field
The invention belongs to oilfield chemistry additive for drilling fluid technical field, be specifically related to a kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent and preparation method thereof.
Background technology
Along with the deficient needs meeting people's productive life again of petroleum resources simultaneously, the exploitation of deep-well and ultra deep well oil gas is become inevitable.But due to deep-well, ultra deep well downhole temperature and pressure higher, stratal configuration more complicated, often high-pressure oil-gas layer and brine layer can be run in drilling process, and people are to drill in fluid unstable properties, filter loss is crossed high technical barrier and is difficult to solve, often can there is down-hole to cave in and the down-hole complex accident such as bit freezing in drilling operation course, great inconvenience is brought to drilling well work, make the hydrocarbon resources of deep formation well can not serve the mankind, therefore researching high-temperature drilling fluid has particularly become an important topic being badly in need of solving to the development of oil field chemical fluid loss agent.
Sulfonated phenol formaldehyde resin (SMP) is a kind of good high temperature resistance, salt resistant filter loss reduction agent, serves vital role to the development of China's deep-well and ultra-deep well drilling work.In drilling fluid, sulfonated phenol formaldehyde resin mainly relies on Van der Waals force to be adsorbed on electronegative clay particle surface, and heat of adsorption is little, and adsorptive capacity is little, but along with the increase of present stage drilling depth, downhole temperature is more and more higher, and adsorption becomes unstable, easy desorption with the rising of drilling fluid temperature.Studied afterwards and improved, and coordinating during use sulfonated phenol formaldehyde resin and add chromium ion (Cr 2+), by the complexing action of metallic cation, the adsorptive capacity of sulfonated phenol formaldehyde resin to clay particle can be made to be significantly improved, thus improve its high temperature resistant property, but introduce heavy metal ion can formation damage, and serious environment pollution, if do not add chromium ion, in on-the-spot application, the addition of sulfonated phenol formaldehyde resin can be very large, there will be that treatment agent utilization ratio is low, waste starting material, high in cost of production problems.
Summary of the invention
The present invention is directed to above-mentioned weak point and a kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent provided and preparation method thereof, this preparation method adopts stepwise process to synthesize the intermediate in differential responses stage, by intermediate resynthesis target product, preparation method is simple, yield is high, cost is low, and the amphoteric acrylamide copolymer high temperature mud fluid loss agent prepared can reach higher temperature resistance, saline-alkaline tolerance when usage quantity is lower.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is:
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent, its preparation method comprises the following steps:
(1) preparation of cationization linear resin
By phenol, formaldehyde, peyocactine in molar ratio 10:10-15:1-2 add in reaction vessel, stir under normal temperature, and be warming up to 70-80 DEG C after 3-4 by hydrochloric acid conditioning solution pH value, stirring and refluxing reaction 60-90min at this temperature, becomes after muddiness until test solution;
(2) preparation of azochlorosulfonate methyl agent
Sodium Pyrosulfite and the distilled water mixing of quality such as to take, drip formaldehyde solution under stirring, after dropwising, bath temperature is risen to 50-60 DEG C, isothermal reaction 4h; Wherein the mol ratio of formaldehyde and Sodium Pyrosulfite is 1.5-2.5:1;
(3) preparation of amphoteric ion type resol
Be that 1:0.8-1.2 mixes by the phenol under molten state and azochlorosulfonate methyl agent with mol ratio, be 9-10 by 20% aqueous sodium hydroxide solution regulator solution pH value, formaldehyde solution is dripped after stirring reaction 40min at 70 DEG C, then 70 DEG C of constant temperature stirring reaction 20min, then cationization linear resin is added, temperature is risen to 95-100 DEG C, isothermal reaction 2-3h, add a certain amount of formaldehyde solution again, isothermal reaction 30min, between the reaction period, maintenance system pH value is 9-10, question response product becomes reddish-brown clear solution, then after being cooled to room temperature, lucifuge drips methyl iodide solution, stirring at room temperature 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent, wherein, add phenol and cationization linear resin mol ratio be 10:1-2, the mol ratio of phenol and formaldehyde total amount is 1:1-2, and the mol ratio of methyl iodide and peyocactine is 3-6:1.
The formaldehyde used in reaction process is the formaldehyde solution that concentration is 36%-40%.
Reaction equation is:
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent provided by the invention and preparation method thereof, has following several beneficial effect:
(1) sulfonated phenol formaldehyde resin (SMP) generally used at present only has anionic group, therefore its application is subject to certain restrictions, invention introduces cation group on sulfonated phenol formaldehyde resin, the existing anionic group of fluid loss agent is made to have cation group again, improve adsorptive capacity and temperature resistance ability, widen the use range of fluid loss agent, be namely extended to deep-well, ultra deep well from middle-deep well.
(2) existing building-up reactions adopts and once feeds intake, all reaction kettle for reaction is joined by all raw materials, this technique is frequently reinforced and speed of reaction is wayward, and the present invention adopts stepwise process namely to synthesize different steps intermediate, then intermediate resynthesis target product is adopted, the invention solves the problem of interference mutually between differential responses, the target substance of specification of quality while improving yield, can be obtained.
(3) adsorptive capacity of electronegative surface of clay is added in the present invention by positively charged ion electrostatic adhesion and adsorption by hydrogen bond, the consumption for the treatment of agent is reduced while keeping drilling fluid high temperature resistance, anti-salt property, be a kind of functional, the novel fluid loss agent of various complicated high temperature deep well can be promoted the use of.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of amphoteric acrylamide copolymer high temperature mud fluid loss agent;
Fig. 2 is the SEM figure that amphoteric acrylamide copolymer high temperature mud fluid loss agent (embodiment 1 sample) amplifies 1000 times;
Fig. 3 is " three sulphur mud " mud cake surface SEM picture under 200 DEG C of conditions after aging 16h of interpolation 5% amphoteric acrylamide copolymer (embodiment 1 sample); Wherein Fig. 3-1 and Fig. 3-3 be " the three sulphur mud " of interpolation 5% amphoteric acrylamide copolymer (embodiment 1 sample) under 200 DEG C of conditions after aging 16h same position, mud cake surface amplify the SEM picture of 2000,5000 times respectively; Fig. 3-2 and Fig. 3-4 be " the three sulphur mud " of interpolation 5% amphoteric acrylamide copolymer (embodiment 1 sample) under 200 DEG C of conditions after aging 16h same position, mud cake surface amplify the SEM picture of 5000,10000 times respectively.
Embodiment
Embodiment 1
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent, its preparation method comprises the following steps:
(1) preparation of cationization linear resin
Get phenol respectively, formaldehyde, peyocactine 10.8g, 9.8g, 2.0g add in reaction vessel, stir under normal temperature, and be warming up to 80 DEG C after 3 by hydrochloric acid conditioning solution pH value, stirring and refluxing reaction 60min, now solution turned cloudy, for subsequent use at this temperature;
(2) preparation of azochlorosulfonate methyl agent
Get 26.5g Sodium Pyrosulfite and 26.5g distilled water mixes, stir and drip 21.2g formaldehyde solution down, bath temperature is risen to 50 DEG C after dropwising, isothermal reaction 4h; Because exothermic heat of reaction, therefore formaldehyde will dropwise add, and can not disposablely add;
(3) preparation of amphoteric ion type resol
Phenol under 25.2g molten state is added in azochlorosulfonate methyl agent prepared by step (2), with 20% aqueous sodium hydroxide solution, system pH is adjusted to 9, formaldehyde solution 17.6g is dripped after stirring reaction 40min at 70 DEG C, after formaldehyde dropwises, 70 DEG C of constant temperature stir 20min, then cationization linear resin prepared by step (1) is added, temperature is risen to 100 DEG C, isothermal reaction 3h, 12.6g formaldehyde solution is added subsequently to system, isothermal reaction to system becomes reddish-brown clear solution, between the reaction period, maintenance system pH value is 9, finally solution is cooled to room temperature, lucifuge drips 7.5mL methyl iodide, stirring at room temperature 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent.
Embodiment 2
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent, its preparation method comprises the following steps:
(1) preparation of cationization linear resin
Get phenol respectively, formaldehyde, peyocactine 16.2g, 15.1g, 28.5g add in reaction vessel, stir under normal temperature, and be warming up to 75 DEG C after 3 by hydrochloric acid conditioning solution pH value, stirring and refluxing reaction 60min at this temperature, now solution turned cloudy, for subsequent use;
(2) preparation of azochlorosulfonate methyl agent
Get 26.5g Sodium Pyrosulfite and 26.5g distilled water mixes, stir and drip 21.2g formaldehyde solution down, bath temperature is risen to 50 DEG C after dropwising, isothermal reaction 4h; Because exothermic heat of reaction, therefore formaldehyde will drip gradually, can not disposablely add;
(3) preparation of amphoteric ion type resol
Phenol under 25.2g molten state is added in azochlorosulfonate methyl agent flask prepared by step (2), with 20% aqueous sodium hydroxide solution, system pH is adjusted to 10, formaldehyde solution 17.6g is dripped after stirring reaction 40min at 70 DEG C, after formaldehyde dropwises, 70 DEG C of constant temperature stir 20min, then cationization linear resin prepared by step (1) is added, temperature is risen to 95 DEG C, isothermal reaction 2h, 12.6g formaldehyde solution is added subsequently to system, isothermal reaction to system becomes reddish-brown clear solution, between the reaction period, maintenance system pH value is 10, finally solution is cooled to room temperature, lucifuge drips 7.5mL methyl iodide, stirring at room temperature 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent.
Embodiment 3
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent, its preparation method comprises the following steps:
(1) preparation of cationization linear resin
Get phenol respectively, formaldehyde, peyocactine 16.2g, 15.1g, 28.5g add in reaction vessel, stir under normal temperature, and be warming up to 70 DEG C after 4 by hydrochloric acid conditioning solution pH value, stirring and refluxing reaction 60min at this temperature, now solution turned cloudy, for subsequent use;
(2) preparation of azochlorosulfonate methyl agent
Get 22.5g Sodium Pyrosulfite and 22.5g distilled water mixes, stir and drip 18.2g formaldehyde solution down, bath temperature is risen to 50 DEG C after dropwising, isothermal reaction 4h; Because exothermic heat of reaction, therefore formaldehyde will drip gradually, can not disposablely add;
(3) preparation of amphoteric ion type resol
Phenol under 21.2g molten state is added in azochlorosulfonate methyl agent flask prepared by step (2), with 20% aqueous sodium hydroxide solution, system pH is adjusted to 10, formaldehyde solution 14.6g is dripped after stirring reaction 40min at 70 DEG C, after formaldehyde dropwises, 70 DEG C of constant temperature stir 20min, then cationization linear resin prepared by step (1) is added, temperature is risen to 100 DEG C, isothermal reaction 2h, 9.6g formaldehyde solution is added subsequently to system, isothermal reaction to system becomes reddish-brown clear solution, between the reaction period, maintenance system pH value is 10, finally solution is cooled to room temperature, lucifuge drips 6.3mL methyl iodide, stirring at room temperature 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent.
Embodiment 4
A kind of amphoteric acrylamide copolymer high temperature mud fluid loss agent, its preparation method comprises the following steps:
(1) preparation of cationization linear resin
Get phenol respectively, formaldehyde, peyocactine 10.8g, 10.1g, 19.0g add in reaction vessel, stir under normal temperature, and be warming up to 70 DEG C after 3 by hydrochloric acid conditioning solution pH value, stirring and refluxing reaction 60min at this temperature, now solution turned cloudy, for subsequent use;
(2) preparation of azochlorosulfonate methyl agent
Get 22.5g Sodium Pyrosulfite and 22.5g distilled water mixes, stir and drip 18.2g formaldehyde solution down, bath temperature is risen to 50 DEG C after dropwising, isothermal reaction 4h; Because exothermic heat of reaction, therefore formaldehyde will drip gradually, can not disposablely add;
(3) preparation of amphoteric ion type resol
Phenol under 23.2g molten state is added in azochlorosulfonate methyl agent flask prepared by step (2), with 20% aqueous sodium hydroxide solution, system pH is adjusted to 10, formaldehyde solution 14.6g is dripped after stirring reaction 40min at 70 DEG C, after formaldehyde dropwises, 70 DEG C of constant temperature stir 20min, then cationization linear resin prepared by step (1) is added, temperature is risen to 100 DEG C, isothermal reaction 3h, 11.6g formaldehyde solution is added subsequently to system, isothermal reaction to system becomes reddish-brown clear solution, between the reaction period, maintenance system pH value is 10, finally solution is cooled to room temperature, lucifuge drips 6.7mL methyl iodide, stirring at room temperature 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent.
Experimental example 1 measures the characteristic group of amphoteric acrylamide copolymer high temperature mud fluid loss agent
Infrared spectroscopy is adopted to characterize, at 4000-400cm the characteristic group in product molecule -1band absorption peak in scope, as shown in Figure 1, characteristic group is embodied in:
(1) at 3430cm -1place is the stretching vibration peak of phenolic hydroxyl group, confirms that product contains a large amount of phenolic hydroxyl structure;
(2) at 2921cm -1near have a less absorption peak to be-CH 2-formation vibration peak, confirms in product containing methylene radical;
(3) at 1190cm -1place is-SO 3 2-the characteristic peak that asymmetrical stretching vibration produces, 1039cm -1place is yes-SO 3 2-the characteristic peak that symmetrical stretching vibration produces, 553cm -1place is the characteristic peak that C-S stretching vibration produces;
(4) at 875cm -1place is the characteristic peak of quaternary ammonium salt N-C stretching vibration, confirms in product structure containing quaternary ammonium salt structure.
Experimental example 2 measures the absorption of amphoteric acrylamide copolymer high temperature mud fluid loss agent in clay particle surface
UV-Vis spectra method is adopted to measure the absorption of amphoteric acrylamide copolymer high temperature mud fluid loss agent sample in clay particle surface.After utilizing UV-Vis Spectrophotometry working sample to adsorb, the concentration of supernatant liquor, calculates the adsorptive capacity of sample in clay particle surface according to langbobier law.
A＝lg(1/T)＝εbc
A 1 A 2 = ϵbc 1 ϵbc 2 = c 1 c 2
A, A in formula 1, A 2-be respectively absorbancy, the absorbancy of solution to be measured, the absorbancy of reference solution;
T-be transmittance, the i.e. ratio of transmitted intensity and incident intensity;
ε-sample optical extinction coefficient at an absorbing wavelength;
B-be absorber thickness, unit centimetre cm;
C, c 1, c 2-being respectively the concentration of extinction material, the concentration of solution to be measured, the concentration of reference solution, unit of gram often rises g/L.
Experimental technique:
1. accurately take 10.00g sample products, with deionized water dissolving, leave standstill 12h after being mixed with 1L solution for subsequent use;
2. get 16 100mL volumetric flasks, weave into one group for every two, one is contrast sample, and another is reference sample; Add the saturated NaCl solution of 20mL to often propping up in volumetric flask, the sample solution then getting finite concentration gradient difference respectively adds in reference numeral volumetric flask, and uses deionized water constant volume, measures absorbancy, production standard curve;
3. add 1g adsorbate (clay) respectively in contrast sample, after manually shaking up, volumetric flask is left standstill 24h, make sample products reach adsorption equilibrium in solution; Often will organize contrast sample centrifugal (the centrifugal 5min of 3000r/min), and get supernatant part, then measure the absorbancy of each sample with ultraviolet-visible pectrophotometer;
4. the adsorptive capacity of sample products on adsorbate (clay) is calculated according to above formula.
Result shows that the saturated extent of adsorption of amphoteric acrylamide copolymer high temperature mud fluid loss agent sample on clay particle is tending towards saturated trend in first to increase afterwards along with the increase of cations, in embodiment 1,2,3,4 adsorptive capacity of sample to clay be respectively 31.7,33.5,25.9,28.5mg/g soil, the adsorptive capacity recording sulfonated-pheno-formoldehyde resin (SMP) under similarity condition is 15mg/g soil.
Experimental example 3 measures the sulfonation degree of amphoteric acrylamide copolymer high temperature mud fluid loss agent
Sulfonation degree is the important indicator ensureing positively charged ion resol good aqueous solubility and high temperature degree of hydration.Sulfonation degree records in sample by volumetry and calculates after S constituent content, with reference to national standard " measuring method of GB2286-1991-T coke total sulphur content ", sample is got 1.00 ~ 2.00g after 60 DEG C of condition vacuum-drying 24h and puts into crucible, the fully oxidized one-tenth sulfate radical of sample sulfite root is made at about 850 DEG C high temperature sinterings, after constant to sample quality, product after calcination is dissolved, filters, adopt volumetry to record the SO of this sample 4 2-content, adds excessive BaCl in sample solution 2solution, SO 4 2-be converted into BaSO 4precipitation, excessive Ba 2+be about in the buffered soln of 10 at pH, use standardized solution titration.The sulfonation degree of sample is calculated finally by lower examination.
n ( - SO 3 2 - ) = n ( SO 4 2 - ) = 96.06 × [ C 1 V 1 - C 2 V 2 ] 5
In formula
C 1refer to BaCl 2the substance withdrawl syndrome of standardized solution, unit is that mmole often rises (mmol/L);
C 2refer to the substance withdrawl syndrome of EDTA standardized solution, unit is that mmole often rises (mmol/L);
V 1refer to BaCl 2the volume of standardized solution, unit is milliliter (mL);
V 2consume the volume of EDTA standardized solution when referring to measure, unit is milliliter (mL)
The sulfonation degree that experiment records sample in embodiment 1,2,3,4 is respectively 83.2%, 80.5%, 75.6%, 74.8%.
Experimental example 4 measures the cloud point salinity of amphoteric acrylamide copolymer high temperature mud fluid loss agent
Can there is turbid phenomenon along with the rising of NaCl concentration in solution in the aqueous solutions of polymers of high density, polymkeric substance is partly dissolved from completely dissolving to become, and when occurring changing, the NaCl concentration of solution is cloud point salinity.The amphoteric acrylamide copolymer aqueous solution of same concentrations is added in the salt solution of different concns, when the salinity of solution is (with Cl -1meter) lower than product cloud point salinity time, the extinction value E of solution has nothing to do with the salinity of solution (pH value of solution should be roughly the same).When saltness in solution reaches or exceed cloud point salinity, solution occurs muddy, E value obviously increases, and the saltness of solution larger E value is also larger, can judge that solution occurs from the noticeable change of E value muddy, determine the cloud point salinity of inventive samples with reference to oil and gas industry standard " SY/T5094-2008 sulfonated-phenoformoldehyde resin for drilling fluid ", its cloud point salinity reduces along with the increase of cation ionization degree, and in embodiment 1,2,3,4, the cloud point salinity of sample is (with Cl -1meter) be respectively 165g/L, 161g/L, 171g/L, 170g/L, all meet the cloud point salt angle value 160g/L of standard.
The filtrate loss controllability evaluation of experimental example 5 pairs of amphoteric acrylamide copolymer high temperature mud fluid loss agents
Experiment adopts " three sulphur mud " system, carries out filtrate loss controllability evaluation with reference to oil and gas industry standard " SY/T5094-2008 sulfonated-phenoformoldehyde resin for drilling fluid " to inventive samples.
Experimental technique:
Base slurry preparation: at 25 ± 3 DEG C, add 0.56g anhydrous sodium carbonate in the high-speed stirring cup filling 350mL distilled water, 14g evaluates soil and the experiment of 14g drilling fluid is native, stirs 20min with high speed agitator.Period interrupts twice and to hang lower wall of container sticks thing, at room temperature curing in airtight condition 24h, is namely mixed with base slurry.Base is starched high-speed stirring 5min, and test base slurry filter loss, its filter loss within the scope of 65 ± 10mL, should suitably can adjust two kinds of native powder dosages, base is starched and meets the requirements, and leaves sombre place in for subsequent use.
Starch and the heat-resistant salt-resistant performance of test experiments slurry according to the formulated experiment of setting, experiment slurry formula:
(1) hyposaline drilling fluid: base slurry+5%SMC+5%SMK+ treatment agent+10%NaCl+2.5%Na 2cO 3;
(2) half saturated brine drilling fluid: base slurry+5%SMC+5%SMK+ treatment agent+20%NaCl+2.5%Na 2cO 3;
(3) saturated salt-water drilling fluid: base slurry+5%SMC+5%SMK+ treatment agent+36%NaCl+2.5%Na 2cO 3;
Sulfonated lignite SMC meets SY/T5092-2002 standard; Sulfonation tannin extract SMK meets SY/T5091-93 standard.
Experimental result shows, the addition of amphoteric acrylamide copolymer be 5% drilling fluid under 200 DEG C of conditions, after aging 16h, record the High Temperature High Pressure filtrate reducing amount (FL of sample in embodiment 1,2,3,4 hTHP) be respectively 22mL, 22mL, 25mL, 24mL, its high temperature resistance high pressure drop leak-off sexual satisfaction standard-required, and be better than existing SMP (﹥ 30mL).
Experimental example 6
By detecting amphoteric acrylamide copolymer high temperature mud fluid loss agent properties of sample of the present invention, known, properties of sample in embodiment 1 is best, therefore, adopt environmental scanning electron microscope (SEM, Quanta450 type) to its product structure, and addition is that " three sulphur mud " mud cake surface under 200 DEG C of conditions after aging 16h of the amphoteric acrylamide copolymer (embodiment 1 sample) of 5% is analyzed.
Amphoteric acrylamide copolymer is macromole three dimensional structure polymkeric substance, is uniformly dispersed in aqueous, as shown in Figure 2.
Mud cake surface results as shown in Figure 3, filter cake smooth surface, compact structure.The mud cake surface compact that the wellbore fluid added is formed under tying up to high saliferous hot conditions and smooth, containing stable, uniform mesh skeleton structure, do not find clay agglomeration phenomena, illustrate that it has stronger adsorption by clay ability and strong hydratability, inhibit clay swelling, improve particles filled effect, the rate of permeation eventually reducing mud cake reaches filtrate reducing effect.

Claims (2)

1. a preparation method for amphoteric acrylamide copolymer high temperature mud fluid loss agent, comprises the following steps:
(1) preparation of cationization linear resin
By phenol, formaldehyde, peyocactine in molar ratio 10:10-15:1-2 add in reaction vessel, stir under normal temperature, and be warming up to 70-80 DEG C, back flow reaction 60-90min after 3-4 by hydrochloric acid conditioning solution pH value; Wherein, the formaldehyde of reaction is participated in be concentration is the formaldehyde solution of 36%-40%;
(2) preparation of azochlorosulfonate methyl agent
Sodium Pyrosulfite and the distilled water mixing of quality such as to take, stir that lower to drip concentration be the formaldehyde solution of 36%-40%, dropwise rear 50-60 DEG C of isothermal reaction 4h; Wherein the mol ratio of formaldehyde and Sodium Pyrosulfite is 1.5-2.5:1;
(3) preparation of amphoteric ion type resol
Be that 1:0.8-1.2 mixes by the phenol under molten state and azochlorosulfonate methyl agent with mol ratio, be 9-10 by 20% aqueous sodium hydroxide solution regulator solution pH value, the formaldehyde solution that concentration is 36%-40% is dripped after 70 DEG C of reaction 40min, then 70 DEG C of isothermal reaction 20min, then cationization linear resin is added, 95-100 DEG C of isothermal reaction 2-3h, add the formaldehyde solution that concentration is 36%-40% again, 95-100 DEG C of isothermal reaction 30min, between the reaction period, maintenance system pH value is 9-10, question response product becomes reddish-brown clear solution, then after being cooled to room temperature, lucifuge drips methyl iodide solution, room temperature reaction 1h, obtain amphoteric acrylamide copolymer high temperature mud fluid loss agent, wherein, add phenol and cationization linear resin mol ratio be 10:1-2, the mol ratio of phenol and formaldehyde total amount is 1:1-2, and the mol ratio of methyl iodide and peyocactine is 3-6:1.
2. the amphoteric acrylamide copolymer high temperature mud fluid loss agent prepared of the method for claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108130057A (en) * 2017-12-30 2018-06-08 周益铭 A kind of preparation method of heat resistant type fluid loss additive
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Publication number Priority date Publication date Assignee Title
CN108130057A (en) * 2017-12-30 2018-06-08 周益铭 A kind of preparation method of heat resistant type fluid loss additive
CN116535587A (en) * 2023-06-13 2023-08-04 石家庄华莱鼎盛科技有限公司 Natural plant polyphenol modified phenolic resin filtrate reducer for drilling fluid
CN116535587B (en) * 2023-06-13 2023-10-27 石家庄华莱鼎盛科技有限公司 Natural plant polyphenol modified phenolic resin filtrate reducer for drilling fluid

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