CN105368423A - Chromium-free composite resin gel-type profile control agent for oil exploitation and preparation method and application thereof - Google Patents
Chromium-free composite resin gel-type profile control agent for oil exploitation and preparation method and application thereof Download PDFInfo
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- C09K8/506—Compositions based on water or polar solvents containing organic compounds
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- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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Abstract
The invention relates to a chromium-free composite resin gel-type profile control agent for oil exploitation. The profile control agent is prepared from a nano-silica modified cross-linked polymer, a stabilizing agent, a reinforcing agent, organic sulfonate, a density modifier, a surface active agent, an additive, a thickening agent, a wetting agent and water. According to the profile control agent, under the synergistic effect of unique modification of raw materials, suitable selection of components, unique steps and technological parameters of a preparation method and the like, the target product with the best effect is obtained; the target product has good mechanical performance, temperature resistance, mineralization resistance, alkali resistance and the like and has good application prospects and industrial potential in the energy exploitation field.
Description
Technical field
The present invention relates in a kind of oilfield exploitation and exploitation and be used for amendment improving petroleum products and preparation method thereof and purposes, relate more particularly to a kind of oil recovery Chrome-free compound resin gel-like amendment and preparation method thereof and purposes, belong to oil gas development technology field.
Background technology
Along with the long-term exploitation of China's oil, the features such as each elephant ubiquity production declining, water oil ratio reduction at present, this proposes urgent requirement to how improving oil production rate.Especially in the middle and later periods of water flooding, due to the nonuniformity on stratum, cause injection water often to advance by leaps and bounds along most permeable zone, it is low that middle low permeability layer involves degree, has a strong impact on the development effectiveness of water drive.
In order to solve these technical problems, people to this has been a large amount of further investigations, and have developed multiple profile control technique.At present, widely used deep flooding fluid amendment mainly contains " the swollen deformed shaped particles of body " and " cross-linked polymer Weak Gels " etc.But these amendments also also exist some defects, such as: the shortcomings such as heat-resistant salt-resistant poor performance, deformability are more weak, anti-shear ability is poor.Based on this real defect, good in the urgent need to research and development chemical stability, can deformation, shear-stable amendment, thus to realize deep rock tunneling technology.
For the profile control technique of other type, scientific research personnel has carried out more patulous research equally, and achieves many achievements, such as:
CN1480627A discloses a kind of Technique for dissecting depth of sludge containing oil in injection well, the component of the amendment used and every 100m
3amendment each component preparation consumption is as follows: emulsifying agent, micella order body pure dry powder, 3-4%; Dispersion agent, 90001 (FO-1) pure dry powder, 0.1-0.4%; Polyacrylamide, molecular weight >1600 ten thousand pure dry powder, 0.2-0.3%; Linking agent, sodium dichromate 99, concentration 99%, 0.8-0.9%; Stablizer, thiocarbamide pure dry powder, 0.1-0.4%; Delayer, oxalic acid, hydrochloric acid are composite, pure dry powder, 0.1-0.2%; Compound anion resin, resin, milk of lime are composite, concentration 99%, 3-5%; Oily sludge, industrial waste, 5-10%.
CN101362940A discloses a kind of profile control agent of injection well.This amendment comprises following ingredients: molecular weight is 100-200 ten thousand, degree of hydrolysis be less than 5% and concentration be the polyacrylamide of 0.5%, concentration is 0.15-0.5% inorganic chromate salt glue crosslinking agent sodium dichromate 99, and concentration is 0.05-0.4% thiocarbamide, and surplus is water.After adopting this amendment, most permeable zone rate of permeation reaches 40-60%, and amendment enters zone of interest ratio can bring up to more than 95% by original 70%.
CN101531890A discloses a kind of preparation method of the amendment for oil field deep temporary blocking, belongs to technical field of petroleum extraction.First resol, organic chromium, Glacial acetic acid, Resorcinol and polyacrylamide are weighed by mass percentage, then the polyacrylamide of weighing slowly to be joined in the water of weighing and to carry out stirring companion, other Delay Action Crosslinker of above-mentioned weighing are added successively, and stirs companion.Amendment for oil field deep temporary blocking prepared by described method, its advantage is that amendment in use gelation time is controlled by adding different linking agents, and gelation time is 8-48 hour; Gelling strength is large, not easily broken glue, and validity period is 1-2; Effectively can change the flow direction of the water filling water on stratum; Formation has extraordinary absorption and ponding.
CN102086385A discloses a kind of organic chromium cross linked gel system defining method based on low molecule high concentration polymer, comprises the following steps: select chromium acetate to be primary cross-linking agent; Select 4,000,000 lower molecular weight high concentration polymers as amendment raw material; The concentration of 4000000 lower molecular weight high concentration polymers is 0.6-0.8%; It is 25-35:1 that primary cross-linking agent gathers double ratio; After plastic, intensity is 190-200mPas.Not only selectivity is strong for it, and formation can not cause permanent injury, and not hinder the carrying out of later stage measure, construction technology is simple.
CN102153999A discloses a kind of zwitter-ion frozen glue amendment, and its mass component is: the amphoteric ion polymer of 0.1-0.3%, this amphoteric ion polymer molecular weight more than 1,500 ten thousand, cationic degree 5-10%, anion degree 5-20%; 0.1-0.3% multiple crosslinking agent, obtain in the following manner, first, phenol and formaldehyde is added by the mass ratio of 1:1 in the enamel reaction still of belt stirrer, after heating to 60 DEG C, add trolamine make phenol and formaldehyde reaction generate one, two, the mixture of trishydroxymethyl phenol, for subsequent use, the amount of the trolamine wherein added is the 1-2% of phenol and formaldehyde gross weight; Secondly, 7-10% sodium dichromate 99 and 10-15% thiocarbamide are added in the reactor of belt stirrer by weight the ratio for 1:1, add hydrochloric acid that concentration is 30-37% again and weight ratio is the sodium-acetate of 1:1 and the mixture of sodium malonate, the amount adding hydrochloric acid is the 1-2% of sodium dichromate 99 and thiocarbamide total amount, the weight ratio of sodium-acetate and sodium malonate mixture and sodium dichromate 99 is 22.5:1, react 12 hours, for subsequent use; The product aforementioned two steps obtained by the mixing of equal-volume ratio, then adds the dehydrated alcohol of gross weight 10-15% as mutual solvent, stirs and obtains multiple crosslinking agent; All the other are water.
CN102174317A discloses a kind of amendment being applicable to ternary composite driving.This amendment comprises following component: concentration is the polyacrylamide of 2000mg/L, and Molecular Weight for Polyacrylamide is 1600-2000 ten thousand, and degree of hydrolysis is 20-25%; Organic chrome cross linker, poly-double ratio 25:1 (W/W); Concentration is the stablizer thiocarbamide of 800mg/L; And the water of surplus; Wherein organic chrome cross linker is made up of chromium trichloride, sodium hydroxide and ammonium lacate mol ratio 1:3:3.Adopt this amendment injection well pressure to rise, main water accepting layer absorbs water relatively, and ratio declines, reservoir producing situation improves, expand swept volume, development contradiction is effectively alleviated, and improves the utilization ratio of chemical flooding, both save fund, turn improve recovery ratio.
CN102504777A discloses a kind of delaying cross-linking polymer hard-gel in-depth profile controlling agent and preparation method thereof, and this amendment consists of by following raw material: anionic polyacrylamide, sodium dichromate 99, S-WAT, sodium salicylate and water; This preparation method, it carries out in the steps below: join in the water of requirement by the anionic polyacrylamide of requirement, after fully dissolving, add the sodium dichromate 99 of requirement, S-WAT, sodium salicylate successively, stir fully and obtain delaying cross-linking polymer hard-gel in-depth profile controlling agent.Achieve following beneficial effect: preparation is simple, stable performance, easy construction, gelation time is long, after plastic, gel-strength is high, achieve long-time, heavy dose of injection at the scene, described delaying cross-linking polymer hard-gel in-depth profile controlling agent is enable to enter the deep of oil reservoir, shutoff preferential path, thus improve waterflooding development effect, improve oil recovery.
CN103333671A discloses a kind of oil field amendment; Be made up of oil field sulfide hydrogen sewage, polymkeric substance, sodium dichromate 99; Oil field sulfide hydrogen concentration of wastewater is 0.1-20mg/L, sodium dichromate 99 add-on is 30-50mg/L, and polymkeric substance add-on is 1500mg/L; When to contain concentration of hydrogen sulfide be 20-50mg/L to oilfield sewage, carry out sudden and violent oxygen to sewage, hydrogen sulfide content is reduced within the scope of 0.1-20mg/L, adds the sodium dichromate 99 of 30-50mg/L, 1500mg/L polymkeric substance; Described amendment has been captured and sulfide hydrogen sewage can not be utilized to be configured to the amendment problem that polymkeric substance is host, capture profile control in the past utilize sulfide hydrogen sewage to be configured can not the problem of plastic, reduce the working concentration of sodium dichromate 99, without the need to using the reductive agent components such as thiocarbamide simultaneously.
CN103694977A discloses a kind of anti-shearing delay cross linking organic profile control agent.Each moiety of this amendment and molarity thereof are: 8,000,000 MW anionic polyacrylamides 0.4-0.6%, sodium dichromate 99 0.1-0.2%, thiocarbamide 0.4-0.6%, S-WAT 0.05%.It achieves gelling strength after stratum is sheared and meets the profile control requirement of Fracture with low permeability stratum, may be controlled to the glue time, meets the requirement of different well spacing oil reservoir, improve recovery ratio by the concentration adjusting stablizer.Overcome existing transfer drive medicament intensity after well immediate vicinity of wellbore is sheared significantly to decline, do not reach the requirement in shutoff crack, the deficiency of Fracture with low permeability stratum profile control requirement cannot be met.
CN103834376A discloses natural occuring bubbles foam frozen glue amendment of a kind of oil field reinjection water preparation and preparation method thereof and application.Described natural occuring bubbles foam frozen glue amendment consists of: polyacrylamide 0.1-0.3%, linking agent 0.1-0.3%, ammonium chloride 2.0%, Sodium Nitrite 1.6%, catalyzer 0.05-0.15%, pore forming material 0.2-0.5%, stablizer 1-5%, and all the other are oil field reinjection water; Described preparation method be first with oil field reinjection water by polyacrylamide amine solvent, then it is even to add other components dissolved.Described natural occuring bubbles foam frozen glue amendment is used for water injection well in oil fields profile control, also can be used for pressure break, acidifying or displacement of reservoir oil volume increase; This foam frozen glue amendment salt resistance is good, the oil field reinjection water dosing of available high salinity high temperature, saving water resource, minimizing oily wastewater pollution; At high temperature the placement long period is not cross-linked, and ensures construction safety; After injecting stratum, foam and frozen glue are cross-linked and are formed simultaneously, and foam is uniformly dispersed in frozen glue, intensity good.
CN104371680A discloses a kind of applicable low permeability oil field produced-water reinjection depth profile control agent, solves the situation that on-the-spot clear water resource is relatively less; Specifically be made up of oilfield produced waste water, host, additive and linking agent, described linking agent is made up of clear water, chromium trichloride, lactic acid and sodium hydroxide, described host mass body volume concentrations is 1500-2500mg/L, the mass body volume concentrations of additive thiocarbamide is 600-1000mg/L, and the crosslinking ratio of host and linking agent is 10:1.Because oilfield produced waste water salinity is between 4000-5000mg/L, being in profile control system is cross-linked within the scope of favourable salinity, if so use oilfield sewage allotment amendment just not need to add the assistant agent such as sodium-chlor, sodium bicarbonate to increase the salinity of sewage, effectively make use of the sewage that oil field produces, improve the suitability of economical effectiveness and amendment formula.
CN104357032A discloses a kind of high temperature resistant secondary crosslinking gel amendment, it is primarily of partially hydrolyzed polyacrylamide, the first linking agent, the second linking agent, conditioning agent and molecule intercalation agent composition, and the mass ratio of above-mentioned five kinds of components is: polypropylene amine: the first linking agent: the second linking agent: conditioning agent: molecule intercalation agent=(80-120): (0.5-1): (260-310): (2-3): (80-100); Described first linking agent is organic chromium, and the second linking agent is that phenol and hexamethylenetetramine synthesize liquid.
CN104403648A discloses a kind of oily sludge base profile modificator, and described 100ml amendment comprises following component: comb-shaped polymer KY-6:100-600mg; First linking agent: comprise urea 1-2.5g and formaldehyde 0.5-2g; Second linking agent: 2-6ml; Emulsifying agent: 1-3ml; Oily sludge: be greater than 0 and be less than or equal to 15g; Water: surplus; Described second linking agent is the mixture of citric acid zirconium, chromium trichloride, Tiorco 677 or three; Optimization citric acid zirconium; Described emulsifying agent is sodium oleate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, tween, Span-80, Span-20, OP-10, AOS or its mixture.
CN104371679A discloses a kind of oil recovery volume expansion grain amendment, the intensity with Water in Water Shutoff in Oil Field profile control particle is high, water-swelling speed is slow, the advantage that resistance toheat is good, the composition of described oil recovery volume expansion grain amendment comprises: wilkinite, perlite, organic chromium gel, calcium carbonate, properties-correcting agent, linking agent and initiator, described properties-correcting agent is sodium carbonate, described linking agent is vinylformic acid, vinyl cyanide, methyl methacrylate or N, N-methylene-bisacrylamide, described initiator is ammonium persulphate, Potassium Persulphate or sodium bisulfite.
CN104449617A discloses a kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent, described anionic polyacrylamide water-in-water emulsion water plugging profile control agent is made up of anionic polyacrylamide water-in-water emulsion and linking agent, linking agent accounts for the 30-150wt% of anionic polyacrylamide water-in-water emulsion, described anionic polyacrylamide water-in-water emulsion is water-soluble nonionic monomer, anionic monomer is at inorganic salt, stablizer, sequestrant, formed by initiator initiated polymerization under the existence of deionized water, described linking agent is resol, one or more in chromium cross linker.
As mentioned above, although disclose the multiple amendment that can be used for Petroleum finance field in prior art, but usually all use chromium cpd in these amendments, which results in the environmental pollution in production process and aftertreatment burden, and also there is the demand that profile control effect needs to be continued improvement.In addition, along with the complicacy day by day of oil well geologic condition and the reduction day by day of oil recovery, urgent demand is had equally for novel amendment.
Consider based on this, how to develop a kind of amendment with premium properties and preparation method thereof, study hotspot just in this field current and emphasis, this technical progress for petroleum prospecting and exploitation has very important industrial value and significance of scientific research, and this also just the basis that is accomplished of the present invention lean on and power place.
Summary of the invention
Based on above-mentioned shortcoming, the present inventor is through concentrating on studies, many defects that amendment in producing for existing Oil/gas Well shows, by further investigation, after having paid a large amount of creative works, thus obtain a kind of novel oil production Chrome-free compound resin gel-like amendment and preparation method thereof and purposes, and then complete the present invention.
Specifically, technical scheme of the present invention and content relate generally to following several aspect.
First aspect, the present invention relates to a kind of oil recovery Chrome-free compound resin gel-like amendment, described amendment comprises nano-silicon dioxide modified cross-linked polymer, stablizer, toughener, organic sulfonate, density adjuster, tensio-active agent, auxiliary agent, thickening material, wetting agent and water.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, with parts by weight, its concrete component concentration is as follows:
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, relate to composition " comprising ", both contained open " comprising ", " comprising " etc. and similar meaning thereof, also contains enclosed " by ... composition " etc. and similar meaning thereof.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described nano-silicon dioxide modified cross-linked polymer is 5-9 part, such as, can be 5 parts, 6 parts, 7 parts, 8 parts or 9 points.
Wherein, described nano-silicon dioxide modified cross-linked polymer prepares according to the method comprised the steps:
A1: the preparation of pre-polymerization cross-linking agent solution, it comprises the steps:
A1-1: the formalin being 37% by phenol and mass percent concentration joins in reactor, is fully uniformly mixed, is then warming up to 70-75 DEG C, obtain reaction soln;
A1-2: add kaoline loaded basic catalyst in reaction soln, and continue stirring reaction 30-40 minute at 70-75 DEG C, then naturally cool to room temperature and filter to isolate catalyzer, filtrate is described pre-polymerization cross-linking agent solution;
A2: degree of hydrolysis is 15-17% and the anion-polyacrylamide that molecular weight is 1400-1600 ten thousand joins in deionized water, is mixed with the anion-polyacrylamide aqueous solution that mass percentage concentration is 5-8%;
A3: under room temperature, modified manometer silicon dioxide micro mist is added in the described anion-polyacrylamide aqueous solution, and under continuous stirring, add the described pre-polymerization cross-linking agent solution (the described pre-polymerization cross-linking agent solution namely obtained in steps A 1-2) obtained in steps A 1, after adding, be warming up to 50-60 DEG C, and stirring reaction 1-2 hour at such a temperature, then gained reacting liquor while hot is poured in the deionized water of 20 DEG C, divide and remove supernatant liquid, obtain spawn, i.e. described nano-silicon dioxide modified cross-linked polymer.
Wherein, in steps A 1-1, the mol ratio of the formaldehyde in phenol and formalin is 0.5-0.9:1, most preferably is 0.75:1.
Wherein, in steps A 1-2, described kaoline loaded basic catalyst is obtained according to the method comprised the steps:
B1: fully ground by kaolin, crosses 400-500 mesh sieve, obtains kaolin powder;
B2: described kaolin powder is calcined 5-6 hour at 700-800 DEG C, is then cooled to room temperature, obtains calcining rear powder;
B3: powder after this calcining being joined volumetric molar concentration is in the NaOH aqueous solution of 3mol/L, and be warming up to 90 DEG C, abundant stirring reaction 2-3 hour at such a temperature, filter, gained powder deionized water is fully washed 2-4 time, last fully dry, obtain described kaoline loaded basic catalyst.
Wherein, in step B3, after described calcining, the mass volume ratio of powder and the NaOH aqueous solution is 1:2-3g/ml, and namely after calcining described in every 1g, powder joins in the described NaOH aqueous solution of 2-3ml.
Wherein, in steps A 1-2, the mass volume ratio of described kaoline loaded basic catalyst and reaction soln is 1:50-70g/ml, namely in reaction soln described in every 50-70ml, adds kaoline loaded basic catalyst described in 1g.
Wherein, in steps A 3, described modified manometer silicon dioxide micro mist is obtained according to the method comprised the steps:
C1: the nano silicon abundant dry 2-4 hour at 150 DEG C by granularity being 5-15nm, obtain dry rear silicon-dioxide;
C2: silicon-dioxide after drying is joined in dehydrated alcohol, fully stirs, then add organo silane coupling agent, and at 50-60 DEG C abundant stirring reaction 60-80 minute, obtain reaction solution;
C3: by reaction solution centrifugation, the solid obtained is in turn with benzene and dehydrated alcohol each abundant washing 2-3 time, and then vacuum-drying, obtains described modified manometer silicon dioxide micro mist.
Wherein, in step C2, the consumption of described dehydrated alcohol is not particularly limited, as long as can be convenient to carrying out and the aftertreatment of reaction, those skilled in the art can carry out suitable selection and determine, are no longer described in detail at this.
Wherein, in step C2, described organo silane coupling agent is hexamethyldisilazane, γ-methacryloxypropyl trimethoxy silane or γ-(2,3-epoxy third oxygen) any one in propyl trimethoxy silicane, most preferably be γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.
Wherein, in step C2, after described drying, the mass ratio of silicon-dioxide and organo silane coupling agent is 1:0.1-0.14, such as, can be 1:0.1,1:0.12 or 1:0.14.
Wherein, in steps A 3, the mass ratio of described modified manometer silicon dioxide micro mist and the described anion-polyacrylamide aqueous solution is 1:10-30, such as, can be 1:10,1:20 or 1:30.
Wherein, in steps A 3, the mass ratio of the described anion-polyacrylamide aqueous solution and described pre-polymerization cross-linking agent solution is 40-50:1, such as, can be 40:1,45:1 or 50:1.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described stablizer is 0.1-0.16 part, such as, can be 0.1 part, 0.13 part or 0.16 part.
Described stablizer is any one in Imarcaptoacetate dioctyltin, Bis(lauroyloxy)dioctyltin, dibutyltin maleate or following formula (I) compound,
Most preferably be described (I) compound.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described toughener is 0.06-0.12 part, such as, can be 0.06 part, 0.08 part, 0.1 part or 0.12 part.
Described toughener is any one in Nonyl pheno (10) ether, Span-80, Laurate alcohol ester phenylacetate, polyoxyethylene polyoxypropylene tetramethylolmethane ether or polypropylene glycerol aether, most preferably is polyoxyethylene polyoxypropylene tetramethylolmethane ether.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described organic sulfonate is 0.15-0.22 part, such as, can be 0.15 part, 0.17 part, 0.19 part, 0.21 part or 0.22 part.
Described organic sulfonate is any one in paratoluenesulfonic acid sodium salt, methylsulphonic acid potassium or n-propyl sodium sulfonate.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described density adjuster is 0.2-0.4 part, such as, can be 0.2 part, 0.25 part, 0.3 part, 0.35 part or 0.4 part.
Described density adjuster is ethylenediamine tetraacetic acid (EDTA) or Sorbitol Powder.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described tensio-active agent is 0.2-0.3 part, such as, can be 0.2 part, 0.25 part or 0.3 part.
Described tensio-active agent is Fatty alcohol polyoxyethylene polyoxypropylene ether, and structural formula is R
1o (C
2h
4o)
p(C
3h
6o)
qh, wherein R
1for C
10-C
18straight or branched alkyl, p is the integer between 4-8, and q is the integer between 4-8.
Such tensio-active agent is very known compound, buys and obtains, be no longer described in detail at this by multiple commercial channel.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described auxiliary agent is 0.05-0.1 part, such as, can be 0.05 part, 0.07 part, 0.09 part or 0.1 part.
Described auxiliary agent is Tiorco 677.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described thickening material is 0.1-0.2 part, such as, can be 0.1 part, 0.15 part or 0.2 part.
Described thickening material is mass ratio is the sodium alginate of 1:2 and the mixture of 2-acrylamido-2-methyl propane sulfonic acid.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described wetting agent is 0.08-0.14 part, such as, can be 0.08 part, 0.1 part, 0.12 part or 0.14 part.
Described wetting agent is Xylo-Mucine, sodium hydroxyethlcellulose or xanthan gum.
In described oil recovery Chrome-free compound resin gel-like amendment of the present invention, the weight part of described water is 30-40 part, such as, can be 30 parts, 35 parts or 40 parts.
As mentioned above, the invention provides a kind of oil recovery Chrome-free compound resin gel-like amendment, described amendment is by the selection of suitable ingredients, and the modification of some component, thus there is the oil recovery effect of multiple excellence, can be applicable to oil production and Exploration Domain, have a good application prospect and industrial production potential.
Second aspect, the invention still further relates to the preparation method of above-mentioned oil recovery Chrome-free compound resin gel-like amendment, described method comprises the steps:
S1: take the nano-silicon dioxide modified cross-linked polymer of respective weight part, stablizer, toughener, organic sulfonate, density adjuster, tensio-active agent, auxiliary agent, thickening material, wetting agent and water respectively.；
S2: the Xiang Shuizhong nano-silicon dioxide modified cross-linked polymer being followed successively by total consumption 80-90%, stablizer, toughener, organic sulfonate, density adjuster and tensio-active agent, and be warming up to 40-50 DEG C, fully stir, until become homogeneous viscous liquid;
S3: the nano-silicon dioxide modified cross-linked polymer adding the 10-20% of auxiliary agent, thickening material, wetting agent and residual content in described homogeneous viscous liquid, continue to stir 30-50 minute, obtain homogeneous viscous liquid, be described oil recovery Chrome-free compound resin gel-like amendment of the present invention.
Described preparation method of the present invention, by suitable preparation process, adding in batches of especially nano-silicon dioxide modified cross-linked polymer, can obtain the object product of good and other excellent effect of stability.
3rd aspect, the present invention relates to the purposes of above-mentioned oil recovery Chrome-free compound resin gel-like amendment in oil production.
Contriver finds that described oil recovery Chrome-free compound resin gel-like amendment has multiple excellent effect, such as have good stability, the effect such as high temperature tolerance, high resistance to salinity, and each composition environmental protection, safety, to environment toxicological harmless or negative effect, can be used to realize various profile control effect, industrialization has a good application prospect and production potential.
As mentioned above, the invention provides a kind of oil recovery Chrome-free compound resin gel-like amendment and its production and use, described amendment passes through selection and the/modification etc. of living of suitable ingredients, and by specific preparation method, thus there is multiple superperformance, in energy development field, there is good industrialization potential.
Accompanying drawing explanation
Accompanying drawing 1 is the Electronic Speculum figure of the spawn (i.e. nano-silicon dioxide modified cross-linked polymer JHW) that preparation example 1 of the present invention obtains.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Reaction example 1: the preparation of kaoline loaded basic catalyst
B1: fully ground by kaolin, crosses 400-500 mesh sieve, obtains kaolin powder;
B2: calcined 5.5 hours at 750 DEG C by described kaolin powder, be then cooled to room temperature, obtains calcining rear powder;
B3: powder after this calcining being joined volumetric molar concentration is in the NaOH aqueous solution of 3mol/L, and be warming up to 90 DEG C, abundant stirring reaction 2.5 hours at such a temperature, filter, gained powder deionized water is fully washed 2-4 time, last fully dry, obtain kaoline loaded basic catalyst, by its called after CAT.
Wherein, in step B3, after described calcining, the mass volume ratio of powder and the NaOH aqueous solution is 1:2.5g/ml.
React routine 1-1: the preparation of kaoline loaded basic catalyst
Except dispensing step B2, the kaolin powder by step B1 directly carries out the reaction of step B3, and other operation is all constant, thus is repeated reaction example 1, obtains preparation example 1-1, by the kaoline loaded basic catalyst called after DCAT obtained.
Reaction example 2: the preparation of modified manometer silicon dioxide micro mist
C1: be the nano silicon of 5-15nm at 150 DEG C fully dry 3 hours by granularity, obtain dry after silicon-dioxide;
C2: joined in appropriate dehydrated alcohol by silicon-dioxide after drying, fully stir, then adds organic machine silane coupling agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, and at 55 DEG C abundant stirring reaction 70 minutes, obtain reaction solution;
C3: by reaction solution centrifugation, the solid obtained is in turn with benzene and dehydrated alcohol each abundant washing 2-3 time, and then vacuum-drying, obtains modified manometer silicon dioxide micro mist, by its called after WF.
Wherein, in step C2, after described drying, the mass ratio of silicon-dioxide and organo silane coupling agent is 1:0.12.
React routine 2-1-2-2: the preparation of nanometer titanium dioxide silicon powder
Except the organic machine silane coupling agent γ-(2 that will react in example 2 step C2,3-epoxy third oxygen) propyl trimethoxy silicane replaces with outside hexamethyldisilazane and γ-methacryloxypropyl trimethoxy silane respectively, other operation is all constant, thus be repeated reaction example 2, obtain reacting routine 2-1 and the routine 2-2 of reaction, by modified manometer silicon dioxide micro mist called after DWF1 and DWF2 respectively obtained.
Preparation example 1: the preparation of nano-silicon dioxide modified cross-linked polymer
A1: the preparation of pre-polymerization cross-linking agent solution, it comprises the steps:
A1-1: the formalin being 37% by phenol and mass percent concentration joins in reactor (mol ratio of the formaldehyde in phenol and formalin is 0.75:1), is fully uniformly mixed, is then warming up to 70 DEG C, obtains reaction soln;
A1-2: add kaoline loaded basic catalyst CAT (mass volume ratio of described kaoline loaded basic catalyst CAT and reaction soln is 1:60g/ml) in reaction soln, and continue stirring reaction 35 minutes at 70 DEG C, then naturally cool to room temperature and filter to isolate catalyzer, filtrate is described pre-polymerization cross-linking agent solution;
A2: degree of hydrolysis is 15-17% and the anion-polyacrylamide that molecular weight is 1,500 ten thousand joins in deionized water, is mixed with the anion-polyacrylamide aqueous solution that mass percentage concentration is 7%;
A3: under room temperature, modified manometer silicon dioxide micro mist WF (mass ratio of described WF and the described anion-polyacrylamide aqueous solution is 1:20) is added in the described anion-polyacrylamide aqueous solution, and under continuous stirring, add the described pre-polymerization cross-linking agent solution (mass ratio of the described anion-polyacrylamide aqueous solution and described pre-polymerization cross-linking agent solution is 45:1) obtained in steps A 1, after adding, be warming up to 55 DEG C, and stirring reaction 1.5 hours at such a temperature, then gained reacting liquor while hot is poured in the deionized water of 20 DEG C, divide and remove supernatant liquid, obtain spawn, be described nano-silicon dioxide modified cross-linked polymer, by its called after JHW.
As can be seen from this JHW Electronic Speculum figure of accompanying drawing 1, what obtain is chain polyacrylamide gel class material, its inner coupling a large amount of nano-silicon dioxide particles (stain wherein), by process so, significantly enhance gel-strength, thus significantly improve its various sealing characteristics.
Preparation example 1-1-1-4: the preparation of nano-silicon dioxide modified cross-linked polymer
Preparation example 1-1: except replacing with except DCAT by the catalyzer in steps A 1-2 by CAT, other operation is all constant, thus is repeated preparation example 1, obtains preparation example 1-1, by the nano-silicon dioxide modified cross-linked polymer called after DJHW1 obtained.
Preparation example 1-2-1-3: replace with respectively except DWF1 and DWF2 except by the modified manometer silicon dioxide micro mist WF in steps A 3, other operation is all constant, thus be repeated preparation example 1, obtain preparation example 1-2 and preparation example 1-3, by nano-silicon dioxide modified cross-linked polymer called after DJHW2 and DJHW3 respectively obtained.
Preparation example 1-4: (namely just granularity is the nano silicon of 5-15nm except being replaced with respectively by the modified manometer silicon dioxide micro mist WF in steps A 3 except nano silicon, and do not carry out the modification of step C1-C3 of the present invention), other operation is all constant, thus be repeated preparation example 1, obtain preparation example 1-2 and preparation example 1-3, by the nano-silicon dioxide modified cross-linked polymer called after DJHW4 obtained.
It should be noted that in following embodiment, each component used in step S2-S3 is each component corresponding taken in step S1.
Embodiment 1: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
S1: take formula (I) compound described in the nano-silicon dioxide modified cross-linked polymer JHW of 5 weight part, 0.1 weight part stablizer, 0.06 weight part toughener polyoxyethylene polyoxypropylene tetramethylolmethane ether, 0.15 weight part organic sulfonate paratoluenesulfonic acid sodium salt, 0.2 weight part density adjuster ethylenediamine tetraacetic acid (EDTA), 0.2 parts surfactant C respectively
12h
25o (C
2h
4o)
4(C
3h
6o)
6h (wherein C
12h
25for dodecyl), 0.05 weight part auxiliary agent Tiorco 677,0.1 parts by weight of thickening agent (for mass ratio is the sodium alginate of 1:2 and the mixture of 2-acrylamido-2-methyl propane sulfonic acid), 0.08 weight part wetting agent Xylo-Mucine and 30 weight parts waters;
S2: Xiang Shuizhong is followed successively by the nano-silicon dioxide modified cross-linked polymer (i.e. 4 weight parts) of total consumption 80%, whole stablizers, whole tougheners, whole organic sulfonates, whole density adjusters and whole tensio-active agents, and be warming up to 40 DEG C, abundant stirring, until become homogeneous viscous liquid;
S3: the nano-silicon dioxide modified cross-linked polymer (i.e. 1 weight part) adding 20% of whole auxiliary agents, whole thickening materials, whole wetting agents and residual content in described homogeneous viscous liquid, continue stirring 30 minutes, obtain homogeneous viscous liquid, obtain oil recovery Chrome-free compound resin gel-like amendment, by its called after TPL1.
Embodiment 2: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
S1: take formula (I) compound described in the nano-silicon dioxide modified cross-linked polymer JHW of 7 weight part, 0.16 weight part stablizer, 0.09 weight part toughener polyoxyethylene polyoxypropylene tetramethylolmethane ether, 0.18 weight part organic sulfonate methylsulphonic acid potassium, 0.4 weight part density adjuster Sorbitol Powder, 0.3 parts surfactant C respectively
16h
33o (C
2h
4o)
6(C
3h
6o)
8h (wherein C
16h
33for n-hexadecyl), 0.07 weight part auxiliary agent Tiorco 677,0.15 parts by weight of thickening agent (for mass ratio is the sodium alginate of 1:2 and the mixture of 2-acrylamido-2-methyl propane sulfonic acid), 0.14 weight part wetting agent sodium hydroxyethlcellulose and 35 weight parts waters;
S2: Xiang Shuizhong is followed successively by the nano-silicon dioxide modified cross-linked polymer (i.e. 6.3 weight parts) of total consumption 90%, whole stablizers, whole tougheners, whole organic sulfonates, whole density adjusters and whole tensio-active agents, and be warming up to 45 DEG C, abundant stirring, until become homogeneous viscous liquid;
S3: the nano-silicon dioxide modified cross-linked polymer (i.e. 0.7 weight part) adding 10% of whole auxiliary agents, whole thickening materials, whole wetting agents and residual content in described homogeneous viscous liquid, continue stirring 40 minutes, obtain homogeneous viscous liquid, obtain oil recovery Chrome-free compound resin gel-like amendment, by its called after TPL2.
Embodiment 3: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
S1: take formula (I) compound described in the nano-silicon dioxide modified cross-linked polymer JHW of 9 weight part, 0.13 weight part stablizer, 0.12 weight part toughener polyoxyethylene polyoxypropylene tetramethylolmethane ether, 0.22 weight part organic sulfonate n-propyl sodium sulfonate, 0.3 weight part density adjuster ethylenediamine tetraacetic acid (EDTA), 0.25 parts surfactant C respectively
18h
37o (C
2h
4o)
8(C
3h
6o)
4h (wherein C
18h
37for Octadecane base), 0.1 weight part auxiliary agent Tiorco 677,0.2 parts by weight of thickening agent (for mass ratio is the sodium alginate of 1:2 and the mixture of 2-acrylamido-2-methyl propane sulfonic acid), 0.11 weight part wetting agent xanthan gum and 40 weight parts waters;
S2: Xiang Shuizhong is followed successively by the nano-silicon dioxide modified cross-linked polymer (i.e. 7.65 weight parts) of total consumption 85%, whole stablizers, whole tougheners, whole organic sulfonates, whole density adjusters and whole tensio-active agents, and be warming up to 50 DEG C, abundant stirring, until become homogeneous viscous liquid;
S3: the nano-silicon dioxide modified cross-linked polymer (i.e. 1.35 weight parts) adding 15% of whole auxiliary agents, whole thickening materials, whole wetting agents and residual content in described homogeneous viscous liquid, continue stirring 50 minutes, obtain homogeneous viscous liquid, obtain oil recovery Chrome-free compound resin gel-like amendment, by its called after TPL3.
Embodiment 4-7: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
Except using the DJHW1-DJHW4 of preparation example 1-1-1-4 respectively and replacing the JHW in embodiment 1-3, other operation is all constant, thus carried out embodiment 4-7 according to the method for embodiment 1-3 respectively, the name of the nano-silicon dioxide modified cross-linked polymer (abbreviation cross-linked polymer) used, embodiment corresponding relation and gained oil recovery Chrome-free compound resin gel-like amendment is as shown in the table.
Embodiment 8-10: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
Except formula (I) compound using following stablizer to replace in embodiment 1-3 respectively, other operation is all constant, thus carried out embodiment 8-10 according to the method for embodiment 1-3 respectively, the name of the stablizer used, embodiment corresponding relation and gained oil recovery Chrome-free compound resin gel-like amendment is as shown in the table.
Embodiment 11-14: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
Except the polyoxyethylene polyoxypropylene tetramethylolmethane ether using following toughener to replace in embodiment 1-3 respectively, other operation is all constant, thus carried out embodiment 11-14 according to the method for embodiment 1-3 respectively, the name of the toughener used, embodiment corresponding relation and gained oil recovery Chrome-free compound resin gel-like amendment is as shown in the table.
Embodiment 15-20: recover the oil with the preparation of Chrome-free compound resin gel-like amendment
Embodiment 15-17: except all nano-silicon dioxide modified cross-linked polymers are added entirely in step s 2 (namely not adding in step S3), other operation is all constant, thus be repeated embodiment 1-3, obtain embodiment 15-17, by oil recovery Chrome-free compound resin gel-like amendment called after TPJ15, TPJ16 and the TPJ17 in turn obtained.
Embodiment 18-20: except all nano-silicon dioxide modified cross-linked polymers are added entirely in step s3 (namely not adding in step S2), other operation is all constant, thus be repeated embodiment 1-3, obtain embodiment 18-20, by oil recovery Chrome-free compound resin gel-like amendment called after TPJ18, TPJ19 and the TPJ20 in turn obtained.
performance test
The following performance test each amendment being carried out to different index, specific as follows.
1, the investigation of sealing characteristics
The concrete steps of this test process are as follows: use simulation fill out sand tube to carry out, first multiple fill out sand tube is at room temperature measured its rate of permeation, then at the uniform velocity pressure injects different amendment of the present invention (relative to every cm of fill out sand tube
2sectional area, injection speed is 0.2ml/ minute, and pressure is 0.1MPa, and injection length is 6 hours); After injection terminates, again measure the rate of permeation of fill out sand tube in the same way, just can calculate the sealing ratiod (sealing ratiod (%)=(before injecting the rear rate of permeation of rate of permeation-injection)/inject front rate of permeation × 100%) of described amendment according to the rate of permeation before the injection of fill out sand tube and after injection, concrete outcome sees the following form:
As seen from the above table: 1, in the preparation method of nano-silicon dioxide modified cross-linked polymer, when the kaolin in the catalyzer used is calcined, the plugging effect of the finished product is caused to have obvious reduction (see TPJ4 data), this proves when calcining kaolin, the catalytic effect of gained catalyzer can be strengthened, thus improve the reaction effect of gained pre-polymerization cross-linking agent solution and anion-polyacrylamide and modified manometer silicon dioxide micro mist, 2, from the data of TPJ5-TPJ6, the organo silane coupling agent used in modified manometer silicon dioxide micro mist preparation method has significant impact for final result, wherein γ-(2, 3-epoxy third oxygen) propyl trimethoxy silicane has best effect, other organo silane coupling agent all causes sealing ratiod to have significantly reducing, reason to fail to be completely contained in chain polyacrylamide gel class material (and to use γ-(2, 3-epoxy third oxygen) propyl trimethoxy silicane time be then included in a large number wherein, see accompanying drawing 1), thus cause the intensity of final gel to have obvious reduction, the final sealing characteristics along with the prolongation of time is so caused to reduce, 3 and when fine silica powder is unmodified (see TPJ7), sealing characteristics reduces the most obvious, has even lost application foundation, 4, from the data of TPJ8-TPJ14, stablizer most preferably is formula (I) compound, toughener most preferably is polyoxyethylene polyoxypropylene tetramethylolmethane ether, and other stablizer and toughener all cause sealing characteristics to decrease, 5 and from TPJ15-TPJ20, when in step S2 or S3 disposable add whole nano-silicon dioxide modified cross-linked polymer time, sealing characteristics also to some extent obviously reduces, this proof ought add fashionable at twice, can make to have between each component to react more thoroughly and/or interact, thus achieve the most excellent plugging effect.
2, the investigation of resistance to salinity
Preparation composite minerals salt solution, wherein the mass percent concentration of various component is as follows: NaCl is 10%, KCl is 5.5%, MgCl
2be 1.5%, CaCl
2be 1%, ZnCl
2be 1.25% and AlCl
3be 1.4%.
Amendment of the present invention is joined in isopyknic above-mentioned composite minerals salt solution, fully stirs, until mixing completely, leaves standstill after 10 days, then measures its sealing characteristics according to above-mentioned identical method, the results are shown in following table:
As can be seen here, amendment TPJ1-TPJ3 of the present invention has good resistance to salinity, even if under so high salinity, still has the high sealing ratiod of 96.7-97.4% after 10 days.And the change of other component, the change etc. of preparation method all cause sealing ratiod to have obvious reduction (and the amplitude of reduction is larger).
3, the investigation of resistance to elevated temperatures
Be encased in high pressure seal tank by amendment of the present invention, under the high temperature of 160 DEG C, heat rolls 24 hours; After end, naturally cool to room temperature, then according to the same procedure in above-mentioned the investigation of sealing characteristics " 1, ", test the sealing characteristics after its pyroprocessing.The results are shown in following table.
As can be seen here, amendment TPJ1-TPJ3 of the present invention has good resistance to elevated temperatures, after heat rolls 24 hours, still there is the sealing ratiod higher than 97%, and TPJ4-TPJ20 has significant reduction, especially it is maximum that the TPJ8-TPJ10 that stablizer changes to some extent reduces amplitude, this demonstrate that the type of stablizer can affect resistance to elevated temperatures significantly.
4, alkaline-resisting investigation
Secure ph is the NaOH aqueous solution of 12.0, is joined in isopyknic NaOH aqueous solution by amendment obtained in above-mentioned the investigation of sealing characteristics " 1, ", fully stirs, until mixing completely, leave standstill after 8 days, then measure its sealing characteristics according to identical method, the results are shown in following table:
As can be seen here, amendment TPJ1-TPJ3 of the present invention has good alkaline resistance properties, leaves standstill after 8 days, still have the sealing ratiod higher than 96%, and TPJ4-TPJ20 has significant reduction in the NaOH alkaline solution of pH value up to 12%.
5, the investigation of tensile strength and elongation at break
Investigate the gel-strength of JHW, DJHW1-DJHW4 obtained above, specific as follows: the thin slice respectively gel JHW, DJHW1-DJHW4 that above-mentioned preparation example obtains being made 0.5cm × 0.5cm × 0.2cm, then at 80 DEG C dry 30 minutes; Install on stretching survey meter after drying terminates, stretch with the speed of 15cm/ minute, till breaking, thus investigated its tensile strength and elongation at break, concrete outcome sees the following form.
As can be seen here, amendment TPJ1-TPJ3 of the present invention has very excellent tensile strength and elongation at break; And DJHW1 all has obvious reduction on this two indices; And the DJHW2-DJHW3 changing organo silane coupling agent reduces more remarkable on this two indices, this again demonstrate the importance of organo silane coupling agent kind.More significantly, DJHW4 reduce amplitude maximum, this demonstrate that to nano silicon carry out modification like this desirable beyond thought technique effect.
As mentioned above, the invention provides a kind of oil recovery and use Chrome-free compound resin gel-like amendment and preparation method thereof and the purposes in the fields such as oil exploitation, drilling well, this amendment is by the synergy of the unique modification to raw material, the suitable selection of component, the distinct steps and processing parameter etc. of preparation method, thus achieve the object product with best effects, there are excellent mechanical property, heat resistance, resistance to salinity and alkaline resistance properties etc., have a good application prospect and industrialization potential in energy extraction field.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. recover the oil with a Chrome-free compound resin gel-like amendment, described amendment comprises nano-silicon dioxide modified cross-linked polymer, stablizer, toughener, organic sulfonate, density adjuster, tensio-active agent, auxiliary agent, thickening material, wetting agent and water.
2. as claimed in claim 1 oil recovery uses Chrome-free compound resin gel-like amendment, and it is characterized in that: with parts by weight, its concrete component concentration is as follows:
3. as claimed in claim 1 or 2 oil recovery uses Chrome-free compound resin gel-like amendment, it is characterized in that: described catalyzer is methanesulfonic.
4. the Chrome-free compound resin gel-like amendment of the oil recovery as described in any one of claim 1-3, is characterized in that: described nano-silicon dioxide modified cross-linked polymer prepares according to the method comprised the steps:
A1: the preparation of pre-polymerization cross-linking agent solution, it comprises the steps:
A1-1: the formalin being 37% by phenol and mass percent concentration joins in reactor, is fully uniformly mixed, is then warming up to 70-75 DEG C, obtain reaction soln;
A1-2: add kaoline loaded basic catalyst in reaction soln, and continue stirring reaction 30-40 minute at 70-75 DEG C, then naturally cool to room temperature and filter to isolate catalyzer, filtrate is described pre-polymerization cross-linking agent solution;
A2: degree of hydrolysis is 15-17% and the anion-polyacrylamide that molecular weight is 1400-1600 ten thousand joins in deionized water, is mixed with the anion-polyacrylamide aqueous solution that mass percentage concentration is 5-8%;
A3: under room temperature, modified manometer silicon dioxide micro mist is added in the described anion-polyacrylamide aqueous solution, and under continuous stirring, add the described pre-polymerization cross-linking agent solution obtained in steps A 1, after adding, be warming up to 50-60 DEG C, and stirring reaction 1-2 hour at such a temperature, then gained reacting liquor while hot is poured in the deionized water of 20 DEG C, point remove supernatant liquid, obtain spawn, i.e. described nano-silicon dioxide modified cross-linked polymer.
5. as claimed in claim 4 oil recovery uses Chrome-free compound resin gel-like amendment, it is characterized in that: described kaoline loaded basic catalyst is obtained according to the method comprised the steps:
B1: fully ground by kaolin, crosses 400-500 mesh sieve, obtains kaolin powder;
B2: described kaolin powder is calcined 5-6 hour at 700-800 DEG C, is then cooled to room temperature, obtains calcining rear powder;
B3: powder after this calcining being joined volumetric molar concentration is in the NaOH aqueous solution of 3mol/L, and be warming up to 90 DEG C, abundant stirring reaction 2-3 hour at such a temperature, filter, gained powder deionized water is fully washed 2-4 time, last fully dry, obtain described kaoline loaded basic catalyst.
6. the Chrome-free compound resin gel-like amendment of the oil recovery as described in claim 4 or 5, is characterized in that: described modified manometer silicon dioxide micro mist is obtained according to the method comprised the steps:
C1: the nano silicon abundant dry 2-4 hour at 150 DEG C by granularity being 5-15nm, obtain dry rear silicon-dioxide;
C2: silicon-dioxide after drying is joined in dehydrated alcohol, fully stirs, then add organo silane coupling agent, and at 50-60 DEG C abundant stirring reaction 60-80 minute, obtain reaction solution;
C3: by reaction solution centrifugation, the solid obtained is in turn with benzene and dehydrated alcohol each abundant washing 2-3 time, and then vacuum-drying, obtains described modified manometer silicon dioxide micro mist.
7. the Chrome-free compound resin gel-like amendment of the oil recovery as described in any one of claim 1-6, it is characterized in that: described stablizer is any one in Imarcaptoacetate dioctyltin, Bis(lauroyloxy)dioctyltin, dibutyltin maleate or following formula (I) compound
Most preferably be described (I) compound.
8. the Chrome-free compound resin gel-like amendment of the oil recovery as described in any one of claim 1-7, it is characterized in that: described toughener is any one in Nonyl pheno (10) ether, Span-80, Laurate alcohol ester phenylacetate, polyoxyethylene polyoxypropylene tetramethylolmethane ether or polypropylene glycerol aether, most preferably is polyoxyethylene polyoxypropylene tetramethylolmethane ether.
9. recover the oil described in any one of claim 1-8 by the preparation method of Chrome-free compound resin gel-like amendment, described method comprises the steps:
S1: take the nano-silicon dioxide modified cross-linked polymer of respective weight part, stablizer, toughener, organic sulfonate, density adjuster, tensio-active agent, auxiliary agent, thickening material, wetting agent and water respectively;
S2: the Xiang Shuizhong nano-silicon dioxide modified cross-linked polymer being followed successively by total consumption 80-90%, stablizer, toughener, organic sulfonate, density adjuster and tensio-active agent, and be warming up to 40-50 DEG C, fully stir, until become homogeneous viscous liquid;
S3: the nano-silicon dioxide modified cross-linked polymer adding the 10-20% of auxiliary agent, thickening material, wetting agent and residual content in described homogeneous viscous liquid, continue to stir 30-50 minute, obtain homogeneous viscous liquid, be described oil recovery Chrome-free compound resin gel-like amendment.
10. the purposes of oil recovery Chrome-free compound resin gel-like amendment in oil production that described in the oil recovery Chrome-free compound resin gel-like amendment according to any one of claim 1-8 or claim 9, preparation method obtains.
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| CN105884158A (en) * | 2016-06-06 | 2016-08-24 | 上海睿岛节能环保科技有限公司 | Oily sludge treatment method based on conditioning technology |
| CN106800921A (en) * | 2016-12-02 | 2017-06-06 | 长江大学 | Wide temperature high salinity adjusts stifled all-round frozen glue |
| CN106800921B (en) * | 2016-12-02 | 2019-06-07 | 长江大学 | The stifled frozen glue of wide temperature high salinity tune |
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| CN112226219B (en) * | 2020-11-10 | 2022-10-28 | 中国石油大学(华东) | Jelly type foam system flow regulating agent and preparation method and application thereof |
| CN112441650A (en) * | 2020-11-12 | 2021-03-05 | 中国石油天然气股份有限公司 | Oil field industrial wastewater recycling method |
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| CN116376533A (en) * | 2023-04-03 | 2023-07-04 | 烟台大学 | External cross-linked temperature-resistant salt-resistant thickening agent |
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