CN106188446A - A kind of modification sulphonation phenolic resin and comprise its treating agent of drilling mud - Google Patents

A kind of modification sulphonation phenolic resin and comprise its treating agent of drilling mud Download PDF

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Publication number
CN106188446A
CN106188446A CN201610562597.8A CN201610562597A CN106188446A CN 106188446 A CN106188446 A CN 106188446A CN 201610562597 A CN201610562597 A CN 201610562597A CN 106188446 A CN106188446 A CN 106188446A
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methyl
phenolic resin
sulfonating agent
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CN106188446B (en
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梁吉营
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Henan Tianfu Chemical Co Ltd
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Henan Tianfu Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52Amides or imides
    • C08F120/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24Condensation 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/032Inorganic additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives

Abstract

The invention provides a kind of modification sulphonation phenolic resin, in parts by weight, it is prepared as follows: (1) adds phenol 1.8 3.2 parts, dihydric phenol 0.9 1.1 parts, 1.5 3 parts of formaldehyde in a kettle., it is warming up to 97 105 DEG C, add 20% hydrochloric acid 0.02 0.06 parts, react 10 15 minutes;(2) it is added thereto to 20% sodium hydroxide solution 0.5 1.3 parts, is subsequently adding sulfonating agent 1.4 1.7 parts, be heated to 97 105 DEG C, react 80 100 minutes;(3) second time adds sulfonating agent 1.4 1.7 parts, 0.02 0.09 parts of formaldehyde, organic polymer nanoparticle 0.03 0.07 parts, silane coupler 0.01 0.05 parts, reacts 80 100 minutes at 97 105 DEG C;(4) third time adds sulfonating agent 1.4 1.7 parts, reacts 80 100 minutes at 97 105 DEG C;Add sulfonating agent 1.4 1.7 parts (5) the 4th times, react 80 100 minutes at 97 105 DEG C;(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin;Present invention also offers the treating agent of drilling mud comprising above-mentioned modification sulphonation phenolic resin.

Description

A kind of modification sulphonation phenolic resin and comprise its treating agent of drilling mud
Technical field
The invention belongs to field of oilfield chemistry, particularly relate to a kind of modification sulphonation phenolic resin, and comprise described modified sulphur Change the treating agent of drilling mud of phenolic resin.
Background technology
Along with the increase of world energy sources demand, World Petroleum Exploration & Development gradually develops to deep formation.Drilling stratum day Become complicated, drilling fluid stability in high temperature and high salinity environment is put forward higher requirement.
Sulfonated phenol formaldehyde resin is the class mud conditioner that developed recently gets up, and has anti-salt, high temperature resistance, the mistake of control mud Water and the performance such as anti-collapse, be used primarily in deep-well brine system.But the sulfonated phenol formaldehyde resin prepared according to existing method is at height When temperature high pressure and high salinity media use, have that service efficiency is low, inhibition is poor and poor in middle-deep well section using effect Defect, high temperature resistance, anti-salt and caving-preventing ability are poor, can not meet saline and saturated salt-water drilling fluid high temperature under ultra-high temperature condition High pressure Filtrate Loss Control and rheol needs.
Therefore, for adapting in drilling process complex environment day by day, need to develop new modification sulphonation phenolic resin and Drilling mud shaking inorganic agent.
Summary of the invention
For solving the problems of the prior art, the invention provides a kind of modification sulphonation phenolic resin, there is the anti-of excellence High temperature, the performance of anti-salt, and the anti-filtration property of excellence.Present invention also offers a kind for the treatment of agent of drilling mud, have anti- High temperature, the function of anti-salt, simultaneously to clay particle thing without flocculation, will not cause thickening power;It is particularly well-suited to deep easy Collapse stratum, salt cream mud bad ground oil-gas Layer probing, free from environmental pollution.
According to an aspect of the invention, it is provided a kind of modification sulphonation phenolic resin, by weight, described modified sulphur Change phenolic resin to be prepared via a method which:
(1) in the reactor be equipped with reflux, it is sequentially added into phenol 1.8-3.2 part, dihydric phenol 0.9-1.1 part, first Aldehyde 1.5-3 part, is warming up to 97-105 DEG C, adds 20% hydrochloric acid 0.02-0.06 part, reacts 10-15 minute;
(2) it is added thereto to 20% sodium hydroxide solution 0.5-1.3 part, is subsequently adding sulfonating agent 1.4-1.7 part, is heated to 97-105 DEG C, reaction 80-100 minute under reflux;
(3) second time adds sulfonating agent 1.4-1.7 part, formaldehyde 0.02-0.09 part, organic polymer nanoparticle 0.03- 0.07 part, silane coupler 0.01-0.05 part, back flow reaction 80-100 minute at 97-105 DEG C;
(4) third time adds sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C;
Add sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C (5) the 4th times;
(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin;
Wherein, consisting of of described sulfonating agent: 18 parts of water, 36.5 parts of formaldehyde, sodium pyrosulfite 45.5 parts.
Described dihydric phenol is one or more in catechol, resorcinol and hydroquinone.
The choosing of described organic polymer nanoparticle freely (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) propylene A kind of monomer polymerization in acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Or the polymer nano-particle that several monomer copolymerization is generated.
Described silane coupler is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl third Ethyl triethoxy silicane alkane, vinyltrimethoxy silane, VTES, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyltrimewasxysilane, 3-isocyanates propyl group three ethoxy One or more in base silane.
The particle diameter of described organic polymer nanoparticle is 20~80nm.
Wherein, in above-mentioned steps (1), hydrochloric acid can be dividedly in some parts, and adds the most in four times.
In above-mentioned steps (2)-(5), period wants many sub-samplings to control viscosity, as viscosity is too high, can suitably add Water goes up to control viscosity.
Modification sulphonation phenolic resin according to the present invention, has the high temperature resistance of anti-excellence, the performance of anti-salt, and excellence Anti-filtration property, is primarily adapted for use in high salinity anti-saturation salt water base mud system, and anti-sodium salt reaches 36%, exceedes at well depth When 7000 meters, using effect is more preferably.Consumption is only about the 50% of similar phenolic resin.
Present invention also offers the preparation method of described modification sulphonation phenolic resin.
By weight, described modification sulphonation phenolic resin is prepared via a method which:
(1) in the reactor be equipped with reflux, it is sequentially added into phenol 1.8-3.2 part, dihydric phenol 0.9-1.1 part, first Aldehyde 1.5-3 part, is warming up to 97-105 DEG C, adds 20% hydrochloric acid 0.02-0.06 part, reacts 10-15 minute;
(2) it is added thereto to 20% sodium hydroxide solution 0.5-1.3 part, is subsequently adding sulfonating agent 1.4-1.7 part, is heated to 97-105 DEG C, reaction 80-100 minute under reflux;
(3) second time adds sulfonating agent 1.4-1.7 part, formaldehyde 0.02-0.09 part, organic polymer nanoparticle 0.03- 0.07 part, silane coupler 0.01-0.05 part, back flow reaction 80-100 minute at 97-105 DEG C;
(4) third time adds sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C;
Add sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C (5) the 4th times;
(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin;
Wherein, consisting of of described sulfonating agent: 18 parts of water, 36.5 parts of formaldehyde, sodium pyrosulfite 45.5 parts.
The implication of described dihydric phenol, organic polymer nanoparticle and silane coupler is described above.
According to another aspect of the present invention, it is provided that a kind for the treatment of agent of drilling mud, by the component group of following weight portion Become:
Modification sulphonation phenolic resin 16-22 part, hydroxypropyl azochlorosulfonate acid sodium 8-12 part, oleamide hydroxy sulfo lycine 6-10 part, Trifluoro propyl methyl cyclotrisiloxane 5-8 part, acrylamide 12-18 part, Ammonium persulfate. 0.02-0.1 part, nano titanium oxide 1- 5 parts, sodium bicarbonate 3-6 part.
Preferably, described treating agent of drilling mud is made up of the component of following weight portion:
18 parts of modification sulphonation phenolic resin, hydroxypropyl azochlorosulfonate acid sodium 10 parts, oleamide hydroxy sulfo lycine 8 parts, trifluoro propyl Methyl cyclotrisiloxane 6 parts, acrylamide 15 parts, Ammonium persulfate. 0.05 part, nano titanium oxide 2 parts, sodium bicarbonate 5 parts.
Wherein, modification sulphonation phenolic resin is prepared according to above-mentioned preparation method.
The raw material producing modification sulphonation phenolic resin is generally phenol and formaldehyde, there is unreacted formaldehyde in product, with Time there is the active group methylol that high temperature can be caused to be thickened in the product, the hydroxypropyl azochlorosulfonate acid sodium that the present invention uses can drop Methylol in low sulfonated phenolic resin, strengthens the hydrophilic of sulfonated phenol formaldehyde resin, it is possible to the high temperature being effectively improved drilling fluid is steady Qualitative.
Oleamide hydroxy sulfo lycine has the structure of chemical formula 1 below, and oleamide hydroxy sulfo lycine is as lubrication breast Agent, the features such as it has, and emulsifying capacity is strong, stable performance, lubricity are good, non-foaming, there is good lubrication drag reduction effect.
[chemical formula 1]
The trifluoro propyl methyl cyclotrisiloxane that the present invention uses has the effect that the filtrate reducing of excellence and retaining wall are anti-collapse Performance;Viscosity effect is little, can adjust the rheological characteristic of drilling fluid well;Temperature resistance ability is strong;Reduce the phase interaction between clay With, effectively prevent the hydration swelling of clay.
Nanometer titanic oxide material, because its Nano Particle relation, can enter the micro-pore of mud shale stratum and split Among seam, thus improve the plugging effect of water-base drilling fluid, expand after slowing down the drilling fluid infiltration to stratum and stratum water suction, fall The trend of block, thus improve borehole wall stability.Additionally, nano titanium oxide can make base slurry form more thin and compact mud cake, Filtrate reducing effect is obvious, and the temperature resistance ability adding the slurry of the base after nano titanium oxide brings up to 200 DEG C from about 120 DEG C.Therefore, Nano titanium oxide, while effectively reducing mud shale permeability, reducing water erosion, is alternatively arranged as a kind of high temperature resistance filtrate reducing Agent uses.
In the present invention, the particle diameter of nano titanium oxide is 20~100nm.
CO in the sodium bicarbonate used in the present invention3 2-、HCO3 -With the Soluble Ca in rock salt stratum2+、Mg2+Occur anti- Should, generate calcium carbonate, magnesium carbonate precipitation, on the one hand eliminate Ca2+、Mg2+Ion, reduces salinity, and this is to a certain extent Eliminate because high salinity reduces the influence factor of other component functioning efficiency;On the other hand the calcium carbonate superfine powder of generation, carbonic acid Magnesium coordinates sealing agent that microcrack mud shale stratum can realize strong closure.
In the present invention, acrylamide and nano titanium oxide occur instead under the effect of sodium bicarbonate and Ammonium persulfate. Should, obtain polyacrylamide nano composite titania material.
Polyacrylamide organic facies and nano titanium oxide inorganic are combined with chemical bonding form by chemical reaction mutually, To high performance drilling fluid additive, reach thickening, filtrate reducing effect, particularly high-temperature resisting and salt-resisting and reservoir protection steady with the borehole wall Fixed effect.
Present invention also offers the preparation method of a kind for the treatment of agent of drilling mud, comprise the following steps:
(1) raw material is prepared by following weight portion
Modification sulphonation phenolic resin 16-22 part, hydroxypropyl azochlorosulfonate acid sodium 8-12 part, oleamide hydroxy sulfo lycine 6-10 part, Trifluoro propyl methyl cyclotrisiloxane 5-8 part, acrylamide 12-18 part, Ammonium persulfate. 0.02-0.1 part, nano titanium oxide 1- 5 parts, sodium bicarbonate 3-6 part;
(2) modification sulphonation phenolic resin is prepared
A () is sequentially added into phenol 1.8-3.2 part, dihydric phenol 0.9-1.1 part, first in the reactor be equipped with reflux Aldehyde 1.5-3 part, is warming up to 97-105 DEG C, adds 20% hydrochloric acid 0.02-0.06 part, reacts 10-15 minute;
B () is added thereto to 20% sodium hydroxide solution 0.5-1.3 part, be subsequently adding sulfonating agent 1.4-1.7 part, be heated to 97-105 DEG C, reaction 80-100 minute under reflux;
C () second time adds sulfonating agent 1.4-1.7 part, formaldehyde 0.02-0.09 part, organic polymer nanoparticle 0.03- 0.07 part, silane coupler 0.01-0.05 part, it is heated to 97-105 DEG C, under reflux reaction 80-100 minute;
D () third time adds sulfonating agent 1.4-1.7 part, be heated to 97-105 DEG C, under reflux reaction 80-100 minute;
E () adds sulfonating agent 1.4-1.7 part the 4th time, be heated to 97-105 DEG C, under reflux reaction 80-100 minute;
F () has been reacted after, spray drying is used to obtain modification sulphonation phenolic resin;
(3) sulfonated phenol formaldehyde resin and hydroxypropyl azochlorosulfonate acid sodium step (2) prepared under agitation mixes, anti-at 50-70 DEG C Answer 10-20 minute;
(4) in the product of step (3), oleamide hydroxy sulfo lycine and trifluoro propyl methyl cyclotrisiloxane are added;
(5) polyacrylamide nano composite titania material is prepared
Acrylamide, nano titanium oxide, sodium bicarbonate and 60-200ml water are joined in reactor, stir, It is subsequently adding Ammonium persulfate., reacts 1-2 hour, then heat to 70-90 DEG C and react 1-2 hour;After reaction terminates, product is through dry Dry obtain polyacrylamide nano composite titania material;
(6) polyacrylamide nano composite titania material prepared by step (5) is joined the product of step (4) In, obtain treating agent of drilling mud.
Wherein, consisting of of described sulfonating agent: 18 parts of water, 36.5 parts of formaldehyde, sodium pyrosulfite 45.5 parts.
Described dihydric phenol is one or more in catechol, resorcinol and hydroquinone.
The choosing of described organic polymer nanoparticle freely (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) propylene A kind of monomer polymerization in acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Or the polymer nano-particle that several monomer copolymerization is generated.
Described silane coupler is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl third Ethyl triethoxy silicane alkane, vinyltrimethoxy silane, VTES, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyltrimewasxysilane, 3-isocyanates propyl group three ethoxy One or more in base silane.
Beneficial effect
1, the modification sulphonation phenolic resin of the present invention is applicable to the water base mud system of fresh water, saline and high salinity, has High temperature resistance, the function of anti-salt, and there is certain anticalcium effect, it is particularly significant that fall High Temperature High Pressure considers vector.
2, using hydroxypropyl azochlorosulfonate acid sodium to enhance the hydrophilic of sulfonated phenol formaldehyde resin, hydration is strong, the bond energy of associated water Height, strengthens the water solublity of sulfonated phenol formaldehyde resin, is effectively improved the high-temperature stability of drilling fluid.
3, make polyacrylamide and nano titanium oxide form composite, reach thickening, filtrate reducing effect, the most anti- The effect of high-temperature salt-resistant and reservoir protection and wellbore stability.
4, the treating agent of drilling mud of the present invention can reach 200 DEG C by temperature resistance, and mud heat stability is strong, changes, safeguards and processes Mud is convenient.
5, the addition of the treating agent of drilling mud of the present invention is generally 1.0-3.0%, and addition is only like product 50%, reduce production cost, decrease again mud usage amount.
6, probing, the reservoir protection such as Yi Ta stratum, deep, salt cream mud bad ground it are particularly well-suited to, free from environmental pollution.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Prepare modification sulphonation phenolic resin
Embodiment 1
(1) in the reactor be equipped with reflux, it is sequentially added into phenol 2.6g, catechol 1.0g, formaldehyde 2.0g, Being warming up to 99 DEG C, add 20% hydrochloric acid 0.03g in four times, react 10 minutes, solution becomes milky;
(2) it is added thereto to 20% sodium hydroxide solution 0.8g, for regulating the pH value of reactant liquor, is subsequently adding sulfonating agent 1.5g, is heated to 99 DEG C, under reflux reaction 90 minutes, and reactant liquor becomes clear;Wherein, consisting of of sulfonating agent: water 18g, formaldehyde 36.5g, sodium pyrosulfite 45.5g;
(3) second time is added thereto to sulfonating agent 1.5g, formaldehyde 0.06g, polymethyl methacrylate nano particle 0.05g, gamma-methyl allyl acyloxypropyl trimethoxysilane 0.03g, back flow reaction 90 minutes at 99 DEG C;
(4) third time adds sulfonating agent 1.5g, back flow reaction 90 minutes at 99 DEG C;
Add sulfonating agent 1.5g, back flow reaction 90 minutes at 99 DEG C (5) the 4th times;
(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin.
Wherein, after every time adding sulfonating agent, the viscosity of timing the most repeatedly sampling monitoring solution, as too high in viscosity can suitably mend Add tap water and go up to control viscosity.
Embodiment 2
(1) in the reactor be equipped with reflux, it is sequentially added into phenol 3.0g, hydroquinone 1.1g, formaldehyde 2.3g, Being warming up to 102 DEG C, add 20% hydrochloric acid 0.05g in four times, react 10 minutes, solution becomes milky;
(2) it is added thereto to 20% sodium hydroxide solution 1.2g, for regulating the pH value of reactant liquor, is subsequently adding sulfonating agent 1.6g, is heated to 102 DEG C, under reflux reaction 90 minutes, and reactant liquor becomes clear;Wherein, consisting of of sulfonating agent: water 18g, formaldehyde 36.5g, sodium pyrosulfite 45.5g;
(3) second time is added thereto to sulfonating agent 1.6g, formaldehyde 0.07g, polystyrene nanoparticle 0.06g, γ-methyl Acryloxypropyl trimethoxy silane 0.04g, back flow reaction 90 minutes at 102 DEG C;
(4) third time adds sulfonating agent 1.6g, back flow reaction 90 minutes at 102 DEG C;
Add sulfonating agent 1.6g, back flow reaction 90 minutes at 102 DEG C (5) the 4th times;
(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin.
Wherein, after every time adding sulfonating agent, the viscosity of timing the most repeatedly sampling monitoring solution, as too high in viscosity can suitably mend Add tap water and go up to control viscosity.
Prepare treating agent of drilling mud
Embodiment 3
(1) sulfonated phenol formaldehyde resin and the 10g hydroxypropyl azochlorosulfonate acid sodium 18g embodiment 1 prepared under agitation mix, at 55 DEG C React 15 minutes;
(2) in the product of step (1), 8g oleamide hydroxy sulfo lycine and 6g trifluoro propyl methyl ring three silica are added Alkane, stirs;
(3) polyacrylamide nano composite titania material is prepared
Joining in reactor by 15g acrylamide, 2g nano titanium oxide, 5g sodium bicarbonate and 100ml water, stirring is all Even;It is subsequently adding 0.05g Ammonium persulfate., reacts 2 hours, then heat to 90 DEG C and react 2 hours;After reaction terminates, product warp It is dried to obtain polyacrylamide nano composite titania material;
(4) polyacrylamide nano composite titania material prepared by step (3) is joined the product of step (2) In, obtain treating agent of drilling mud.
Embodiment 4
(1) modification sulphonation phenolic resin and 10g hydroxypropyl azochlorosulfonate acid sodium 20g embodiment 2 prepared under agitation mixes, 60 DEG C are reacted 15 minutes;
(2) in the product of step (1), 6g oleamide hydroxy sulfo lycine and 8g trifluoro propyl methyl ring three silica are added Alkane, stirs;
(3) polyacrylamide nano composite titania material is prepared
Joining in reactor by 16g acrylamide, 3g nano titanium oxide, 4g sodium bicarbonate and 100ml water, stirring is all Even;It is subsequently adding 0.03g Ammonium persulfate., reacts 2 hours, then heat to 85 DEG C and react 2 hours;After reaction terminates, product warp It is dried to obtain polyacrylamide nano composite titania material;
(4) polyacrylamide nano composite titania material prepared by step (3) is joined the product of step (2) In, obtain treating agent of drilling mud.
Comparative example
Prepare sulfonated phenol formaldehyde resin
Comparative example 1
(1) phenol 1 mole, 1 mole of formaldehyde and 0.1 molar sodium hydroxide are sequentially added into the reflux cooling with blender In the reactor of device, 119 DEG C are stirred 10 minutes, and cooling maintains the temperature at 109 DEG C, is then sequentially added into 1 mole of formaldehyde, Jiao Ya 0.5 mole of sodium sulfate, water 40ml are 3 hours as sulfonating agent, sulfonation time, are eventually adding 1 moles of formaldehyde, at 97 DEG C-104 DEG C Lower back flow reaction 3-4 hour;
(2) viscosity B coefficent of observing response thing at any time, the most suitably supplements water;
(3) at the end of reaction, cooling, it is cooled to 60 DEG C of-70 DEG C of dischargings;
(4) it is dried, obtains sulfonated phenol formaldehyde resin.
Prepare treating agent of drilling mud
Comparative example 2
In addition to not using hydroxypropyl azochlorosulfonate acid sodium, prepare treating agent of drilling mud according to the same manner as in Example 3.
Comparative example 3
In addition to not using trifluoro propyl methyl cyclotrisiloxane, prepare drilling well according to the same manner as in Example 3 Mud conditioner.
Comparative example 4
In addition to not using acrylamide, Ammonium persulfate. and titanium dioxide, prepare according to the same manner as in Example 3 Treating agent of drilling mud.
Wherein, embodiment 1-2 is prepared according to the methods of the invention modification sulphonation phenolic resin;Comparative example 1 is basis Sulfonated phenol formaldehyde resin prepared by routine techniques.Comparative example 2-4 is to omit the brill obtained by one or more compositions in embodiment 3 Well mud conditioner.
The sulfonated phenol formaldehyde resin below prepared by embodiment 1-2 and comparative example 1 and embodiment 3-4 and comparative example 2-4 system Standby treating agent of drilling mud performance is tested.
Base is starched: bentonite 4.5 weight portion, soda 0.5 weight portion, water 100 weight portion.
In above-mentioned base is starched, add product prepared by embodiment of the present invention 1-2, embodiment 3-4 and comparative example 1-4 of 2%, Stir.According to GB/T 16783.1-2006 standard, apparent viscosity, plastic viscosity, the yield value of testing experiment slurry, ingress Power/10-minute gel strength, static filtration and high temperature and high pre ssure filtration.Properties test result is shown in Table 1.
Table 1
From the results shown in Table 1, according to the treating agent of drilling mud of the present invention, there is good high temperature resistance stability And rheological property, it is particularly significant that fall High Temperature High Pressure considers vector, it is possible to meets quick, safety and efficient drilling well requirement.

Claims (9)

1. a modification sulphonation phenolic resin, by weight, described modification sulphonation phenolic resin is to be prepared via a method which :
(1) in the reactor be equipped with reflux, it is sequentially added into phenol 1.8-3.2 part, dihydric phenol 0.9-1.1 part, formaldehyde 1.5-3 part, is warming up to 97-105 DEG C, adds 20% hydrochloric acid 0.02-0.06 part, reacts 10-15 minute;
(2) it is added thereto to 20% sodium hydroxide solution 0.5-1.3 part, is subsequently adding sulfonating agent 1.4-1.7 part, is heated to 97- 105 DEG C, reaction 80-100 minute under reflux;
(3) second time adds sulfonating agent 1.4-1.7 part, formaldehyde 0.02-0.09 part, organic polymer nanoparticle 0.03-0.07 Part, silane coupler 0.01-0.05 part, back flow reaction 80-100 minute at 97-105 DEG C;
(4) third time adds sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C;
Add sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C (5) the 4th times;
(6), after having reacted, spray drying is used to obtain modification sulphonation phenolic resin;
Wherein, consisting of of described sulfonating agent: 18 parts of water, 36.5 parts of formaldehyde, sodium pyrosulfite 45.5 parts.
Modification sulphonation phenolic resin the most according to claim 1, wherein, described dihydric phenol is selected from catechol, isophthalic One or more in diphenol and hydroquinone.
Modification sulphonation phenolic resin the most according to claim 1, wherein, the choosing of described organic polymer nanoparticle is freely (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acryloyl The polymer nano-particle that a kind of monomer in amine, styrene, sodium p styrene sulfonate is polymerized or several monomer copolymerization is generated.
Modification sulphonation phenolic resin the most according to claim 1, wherein, described silane coupler is selected from γ-methyl-prop Alkene monomethacryloxypropyl trimethoxy silane, gamma-methyl allyl acyloxypropyl triethoxysilane, vinyltrimethoxy silane, second Thiazolinyl triethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-(+)-2,3-Epoxy-1-propanol One or more in epoxide propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane.
5. a treating agent of drilling mud, is made up of the component of following weight portion:
Modification sulphonation phenolic resin 16-22 part described in claim 1-4,
Hydroxypropyl azochlorosulfonate acid sodium 8-12 part,
Oleamide hydroxy sulfo lycine 6-10 part,
Trifluoro propyl methyl cyclotrisiloxane 5-8 part,
Acrylamide 12-18 part,
Ammonium persulfate. 0.02-0.1 part,
Nano titanium oxide 1-5 part,
Sodium bicarbonate 3-6 part.
Treating agent of drilling mud the most according to claim 5, is made up of the component of following weight portion:
18 parts of modification sulphonation phenolic resin,
Hydroxypropyl azochlorosulfonate acid sodium 10 parts,
Oleamide hydroxy sulfo lycine 8 parts,
Trifluoro propyl methyl cyclotrisiloxane 6 parts,
Acrylamide 15 parts,
Ammonium persulfate. 0.05 part,
Nano titanium oxide 2 parts,
Sodium bicarbonate 5 parts.
7. according to the treating agent of drilling mud described in claim 5 or 6, wherein, the particle diameter of nano titanium oxide be 20~ 100nm。
8. a preparation method for the treating agent of drilling mud described in claim 5, including:
(1) sulfonated phenol formaldehyde resin is prepared
A () is sequentially added into phenol 1.8-3.2 part, dihydric phenol 0.9-1.1 part, formaldehyde in the reactor be equipped with reflux 1.5-3 part, is warming up to 97-105 DEG C, adds 20% hydrochloric acid 0.02-0.06 part, reacts 10-15 minute;
B () is added thereto to 20% sodium hydroxide solution 0.5-1.3 part, be subsequently adding sulfonating agent 1.4-1.7 part, be heated to 97- 105 DEG C, reaction 80-100 minute under reflux;
C () second time adds sulfonating agent 1.4-1.7 part, formaldehyde 0.02-0.09 part, organic polymer nanoparticle 0.03-0.07 Part, silane coupler 0.01-0.05 part, back flow reaction 80-100 minute at 97-105 DEG C;
D () third time adds sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C;
E () adds sulfonating agent 1.4-1.7 part, back flow reaction 80-100 minute at 97-105 DEG C the 4th time;
F () has been reacted after, spray drying is used to obtain modification sulphonation phenolic resin;
Wherein, consisting of of described sulfonating agent: 18 parts of water, 36.5 parts of formaldehyde, sodium pyrosulfite 45.5 parts;
(2) modification sulphonation phenolic resin and hydroxypropyl azochlorosulfonate acid sodium step (1) prepared under agitation mixes, anti-at 50-70 DEG C Answer 10-20 minute;
(3) in the product of step (2), oleamide hydroxy sulfo lycine and trifluoro propyl methyl cyclotrisiloxane are added;
(4) polyacrylamide nano composite titania material is prepared
Acrylamide, nano titanium oxide, sodium bicarbonate and 60-200ml water are joined in reactor, stirs, then Add Ammonium persulfate., react 1-2 hour, then heat to 70-90 DEG C and react 1-2 hour;After reaction terminates, product drying obtains To polyacrylamide nano composite titania material;
(5) polyacrylamide nano composite titania material prepared by step (4) is joined in the product of step (3), To treating agent of drilling mud.
9. according to the preparation method described in claim, wherein,
Described dihydric phenol is one or more in catechol, resorcinol and hydroquinone;
The choosing of described organic polymer nanoparticle freely (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) acrylic acid second A kind of monomer polymerization or several in ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Plant the polymer nano-particle that monomer copolymerization is generated
Described silane coupler is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl three Ethoxysilane, vinyltrimethoxy silane, VTES, gamma-amino propyl trimethoxy silicane, γ- Aminopropyltriethoxywerene werene, γ-glycidoxypropyltrimewasxysilane, 3-isocyanates propyl-triethoxysilicane One or more in alkane.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130361A (en) * 2014-08-13 2014-11-05 江苏苏博特新材料股份有限公司 Preparation method of highly-sulfonated and highly-concentrated aliphatic superplasticizer
CN104788634A (en) * 2015-05-08 2015-07-22 天津中油渤星工程科技有限公司 Preparation method of high-temperature-resistant modified sulfonated phenol formaldehyde resin for drilling fluids
CN104892877A (en) * 2015-06-09 2015-09-09 中国林业科学研究院林产化学工业研究所 Phenolated lignin modified expandable resorcinol-phenol-formaldehyde resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130361A (en) * 2014-08-13 2014-11-05 江苏苏博特新材料股份有限公司 Preparation method of highly-sulfonated and highly-concentrated aliphatic superplasticizer
CN104788634A (en) * 2015-05-08 2015-07-22 天津中油渤星工程科技有限公司 Preparation method of high-temperature-resistant modified sulfonated phenol formaldehyde resin for drilling fluids
CN104892877A (en) * 2015-06-09 2015-09-09 中国林业科学研究院林产化学工业研究所 Phenolated lignin modified expandable resorcinol-phenol-formaldehyde resin and preparation method thereof

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