CN105368423B - One kind is recovered the oil and uses Chrome-free compound resin gel-like profile control agent and preparation method and purposes - Google Patents
One kind is recovered the oil and uses Chrome-free compound resin gel-like profile control agent and preparation method and purposes Download PDFInfo
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- CN105368423B CN105368423B CN201510665156.6A CN201510665156A CN105368423B CN 105368423 B CN105368423 B CN 105368423B CN 201510665156 A CN201510665156 A CN 201510665156A CN 105368423 B CN105368423 B CN 105368423B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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Abstract
The present invention relates to a kind of oil recovery Chrome-free compound resin gel-like profile control agent, the profile control agent includes nano-silicon dioxide modified cross-linked polymer, stabilizer, reinforcing agent, organic sulfonate, density adjuster, surfactant, auxiliary agent, thickener, wetting agent and water.The synergy that the profile control agent passes through unique modification to raw material, appropriately selected, preparation method the distinct steps of component and technological parameter etc., so as to achieve the purpose product with best effects, with excellent mechanical performance, heat resistance, resistance to salinity and alkaline resistance properties etc., had a good application prospect in energy extraction field and industrialization potential.
Description
Technical field
The present invention relates to a kind of oilfield exploitation be used for improving in exploitation profile control agent and preparation method thereof of oil product with
Purposes, relate more particularly to a kind of oil recovery Chrome-free compound resin gel-like profile control agent and preparation method thereof and purposes, belong to oil
Gas development technique field.
Background technology
With the long-term exploitation of China's oil, the spies such as each elephant generally existing yield declines at present, oil-water ratio reduces
Point, this proposes urgent requirement to how to improve oil exploitation rate.Especially in the middle and later periods of water flooding, due to ground
The anisotropism of layer, cause to inject water and often advanced by leaps and bounds along high permeability zone, middle less permeable layer involves that degree is low, has a strong impact on opening for water drive
Send out effect.
In order to solve these technical problems, people have carried out substantial amounts of further investigation to this, and have developed a variety of profile controls
Technology.At present, widely used deep flooding fluid profile control agent mainly has " the swollen deformed shaped particles of body " and " cross-linked polymer Weak Gels " etc..
But these profile control agents are there is also some defects, such as：Heat-resistant salt-resistant poor performance, deformability are weaker, anti-shear ability compared with
The shortcomings of poor.Based on the real defect, there is an urgent need to research and develop chemical stability it is good, can deformation, resistant to shearing profile control agent, from
And to realize deep rock tunneling technology.
For other types of profile control technique, scientific research personnel has equally carried out more patulous researchs, and achieves many
Achievement, such as：
CN1480627A discloses a kind of Technique for dissecting depth of sludge containing oil in injection well, the component of used profile control agent and
Per 100m3It is as follows that profile control agent each component prepares dosage：Emulsifying agent, micella mesh body pure dry powder, 3-4%；Dispersant, 90001 (FO-
1) pure dry powder, 0.1-0.4%；Polyacrylamide, molecular weight>16000000 pure dry powders, 0.2-0.3%；Crosslinking agent, sodium dichromate,
Concentration 99%, 0.8-0.9%；Stabilizer, thiocarbamide pure dry powder, 0.1-0.4%；Delayer, oxalic acid, hydrochloric acid compounding, pure dry powder,
0.1-0.2%；Compound anion resin, resin, milk of lime compounding, concentration 99%, 3-5%；Oily sludge, industrial waste, 5-
10%.
CN101362940A discloses a kind of profile control agent of injection well.The profile control agent includes following ingredients：Molecular weight is
The polyacrylamide that 100-200 ten thousand, degree of hydrolysis are less than 5% and concentration is 0.5%, concentration join for 0.15-0.5% inorganic chromate salts glue
Agent sodium dichromate, concentration are 0.05-0.4% thiocarbamides, and surplus is water.40- is reached using high permeability zone permeability after the profile control agent
60%, profile control agent, which enters purpose stratum proportion, to bring up to more than 95% by original 70%.
CN101531890A discloses a kind of preparation method of the profile control agent for oil field deep temporary blocking, belongs to oil exploitation
Technical field.Phenolic resin, Organic Chromium, glacial acetic acid, resorcinol and polyacrylamide are weighed by mass percentage first, so
The polyacrylamide of weighing is slowly added into the water of weighing afterwards and carries out stirring companion, by other Delay Action Crosslinkers of above-mentioned weighing
Sequentially add, and stir companion.Profile control agent for oil field deep temporary blocking prepared by methods described, its advantage is different by adding
Crosslinking agent, gelation time is controllable when in use for profile control agent, and gelation time is 8-48 hours；Gelling strength is big, not fragile glue, effectively
Phase is 1-2；The flow direction of the water filling water on stratum can effectively be changed；There are extraordinary absorption and ponding to stratum.
CN102086385A discloses a kind of Organic Chromium cross-linked gel system based on low molecule high concentration polymer and determined
Method, comprise the following steps：It is primary cross-linking agent from chromium acetate；From 4,000,000 low molecule amount high concentration polymers as tune
Cut open agent raw material；The concentration of 4000000 low molecule amount high concentration polymers is 0.6-0.8%；The poly- double ratio of primary cross-linking agent is 25-35:
1；Intensity is 190-200mPas after plastic.Not only selectivity is strong for it, and permanent injury will not be caused to stratum, and not
The progress of obstruction later stage measure, construction technology are simple.
CN102153999A discloses a kind of amphion frozen glue profile control agent, and its mass component is：0.1-0.3% both sexes
Ionomer, the amphoteric ion polymer molecular weight is more than 15,000,000, cationic degree 5-10%, anion degree 5-20%；
0.1-0.3% multiple crosslinking agents, are made in the following manner, first, 1 are pressed in the enamel reaction still of belt stirrer:1 quality
Than adding phenol and formaldehyde, after heating to 60 DEG C, adding triethanolamine makes phenol react one, two, three hydroxyls of generation with formaldehyde
The mixture of sylvan, it is standby, wherein the amount of the triethanolamine added is phenol and the 1-2% of formaldehyde gross weight；Secondly, by 7-
10% sodium dichromate and 10-15% thiocarbamides are 1 by weight:1 ratio is added in the reactor of belt stirrer, adds concentration
Hydrochloric acid and weight ratio for 30-37% are 1:1 sodium acetate and the mixture of sodium malonate, the amount for adding hydrochloric acid are sodium dichromate
With the 1-2% of thiocarbamide total amount, sodium acetate and the weight of sodium malonate mixture and sodium dichromate ratio are 22.5:1, reaction 12 is small
When, it is standby；The product that foregoing two step obtains is added into gross weight 10-15% absolute ethyl alcohol conduct by isometric than mixing
Mutual solvent, stir and produce multiple crosslinking agent；Remaining is water.
CN102174317A discloses a kind of profile control agent suitable for ternary composite driving.The profile control agent includes following component：
Concentration is 2000mg/L polyacrylamide, and Molecular Weight for Polyacrylamide is 1600-2000 ten thousand, degree of hydrolysis 20-25%；It is organic
Chromium cross linker, poly- double ratio 25:1(W/W)；Concentration is 800mg/L stabilizer thiocarbamide；And the water of surplus；Wherein Organic Chromium is handed over
Join agent by chromium trichloride, sodium hydroxide and lactic acid in molar ratio 1:3:3 compositions.Risen using the profile control agent injection well pressure, be main
Want water accepting layer to be improved with respect to the decline of water suction ratio, reservoir producing situation, expand swept volume, development contradiction obtains effectively
Alleviate, improve the utilization rate of chemical flooding, both save fund, improve recovery ratio again.
CN102504777A discloses a kind of delaying cross-linking polymer hard-gel in-depth profile controlling agent and preparation method thereof, the tune
Cut open agent is by following raw materials composition：PAMA, sodium dichromate, sodium sulfite, sodium salicylate and water；The preparation side
Method, it is carried out in the steps below：The PAMA of requirement is added in the water of requirement, treated fully molten
Xie Hou, the sodium dichromate, sodium sulfite, sodium salicylate of requirement are sequentially added, delayed cross-linking polymerization is obtained after stirring fully
The strong gel deep electrical structure of thing.Achieve following beneficial effect：Prepare simple, stable performance, easy for construction, gelation time
Long, gel strength is high after plastic, realizes injection for a long time, heavy dose of at the scene, the delayed cross-linking polymer is coagulated by force
Glue deep electrical structure can enter the deep of oil reservoir, block preferential path, so as to improve waterflooding development effect, improve oil reservoir and adopt
Yield.
CN103333671A discloses a kind of oil field profile control agent；By oil field sulfide hydrogen sewage, polymer, sodium dichromate
Composition；Oil field sulfide hydrogen concentration of wastewater is 0.1-20mg/L, sodium dichromate addition is 30-50mg/L, polymer addition
For 1500mg/L；When it is 20-50mg/L that oilfield sewage, which contains concentration of hydrogen sulfide, sudden and violent oxygen, hydrogen sulfide content drop are carried out to sewage
It is low to the sodium dichromate in the range of 0.1-20mg/L, adding 30-50mg/L, 1500mg/L polymer；The profile control agent is captured
Sulfide hydrogen sewage can not be utilized to configure the profile control agent problem using polymer as host, capture conventional profile control and utilized sulfide hydrogen
Sewage carries out the problem of configuration is unable to plastic, while reduces the concentration of sodium dichromate, without using reducing agents such as thiocarbamides
Component.
CN103694977A discloses a kind of anti-shearing delay crosslinking organic profile control agent.Each constituent of the profile control agent and
Its molarity is：8000000 MW anionic polyacrylamides 0.4-0.6%, sodium dichromate 0.1-0.2%, thiocarbamide
0.4-0.6%, sodium sulfite 0.05%.It realizes the gelling strength after stratum is sheared and meets that Fracture with low permeability stratum profile control will
Ask, the concentration by adjusting stabilizer may be controlled to the glue time, meet different well spacing oil reservoir requirements, improve recovery ratio.Overcome
The existing transfer drive medicament intensity after well near wellbore zone is sheared significantly declines, and does not reach the requirement in closure crack, can not
Meet the deficiency of Fracture with low permeability stratum profile control requirement.
CN103834376A discloses a kind of natural occuring bubbles foam frozen glue profile control agent prepared with oil field reinjection water and its preparation
Method and application.The natural occuring bubbles foam frozen glue profile control agent forms：Polyacrylamide 0.1-0.3%, crosslinking agent 0.1-
0.3%, ammonium chloride 2.0%, natrium nitrosum 1.6%, catalyst 0.05-0.15%, foaming agent 0.2-0.5%, stabilizer 1-
5%, remaining is oil field reinjection water；The preparation method is, first with oil field reinjection water by polyacrylamide amine solvent, adds other
Component is uniformly dissolved.The natural occuring bubbles foam frozen glue profile control agent is used for water injection well in oil fields profile control, it may also be used for pressure break, acidifying or drive
Oil volume increase；The foam frozen glue profile control agent salt-resistance is good, the oil field reinjection water of high salinity high temperature can be used to match somebody with somebody liquid, saving water resource,
Reduce oily wastewater pollution；The placement long period is not crosslinked at high temperature, ensures construction safety；Foam is crosslinked with frozen glue after injecting stratum
Formed simultaneously, foam is uniformly dispersed in frozen glue, intensity is good.
CN104371680A discloses a kind of suitable low permeability oil field produced-water reinjection depth profile control agent, solves live clear water
The relatively small number of situation of resource；Specifically it is made up of oilfield produced waste water, host, additive and crosslinking agent, the crosslinking agent is by clear
Water, chromium trichloride, lactic acid and sodium hydroxide composition, the host mass-volume concentration is 1500-2500mg/L, additive thiocarbamide
Mass-volume concentration be 600-1000mg/L, the crosslinking ratio of host and crosslinking agent is 10:1.Because of oilfield produced waste water salinity
Between 4000-5000mg/L, it is crosslinked in profile control system in the range of favourable salinity, if so adjusted using oilfield sewage
Avoid the need for adding the assistant agents such as sodium chloride, sodium acid carbonate with profile control agent to increase the salinity of sewage, be effectively utilized oil field production
Raw sewage, improve economic effect and the applicability of profile control agent prescription.
CN104357032A discloses a kind of high temperature resistant secondary crosslinking gel profile control agent, and it is mainly by partial hydrolysis polypropylene
Acid amides, the first crosslinking agent, the second crosslinking agent, conditioning agent and molecule intercalation agent composition, the mass ratio of above-mentioned five kinds of components are：Poly- third
Enamine:First crosslinking agent:Second crosslinking agent:Conditioning agent:Molecule intercalation agent=(80-120):(0.5-1):(260-310):(2-
3):(80-100)；First crosslinking agent is Organic Chromium, and the second crosslinking agent is phenol and hexamethylenetetramine Synthesis liquid.
CN104403648A discloses a kind of oily sludge base profile modificator, and the 100ml profile control agents include following components：Combed
Polymer KY-6：100-600mg；First crosslinking agent：Including urea 1-2.5g and formaldehyde 0.5-2g；Second crosslinking agent：2-6ml；
Emulsifying agent：1-3ml；Oily sludge：It is less than or equal to 15g more than 0；Water：Surplus；Second crosslinking agent is citric acid zirconium, trichlorine
Change chromium, aluminium citrate or the mixture of three；Optimization citric acid zirconium；The emulsifying agent be enuatrol, neopelex,
Dodecyl sodium sulfate, tween, Span-80, Span-20, OP-10, AOS or its mixture.
CN104371679A discloses a kind of oil recovery volume expansion grain profile control agent, has the intensity of Water in Water Shutoff in Oil Field profile control particle
The advantages of height, water swelling speed is slow, and heat resistance is good, the composition of the oil recovery volume expansion grain profile control agent include：Bentonite,
Perlite, Organic Chromium gel, calcium carbonate, modifying agent, crosslinking agent and initiator, the modifying agent are sodium carbonate, the crosslinking agent
For acrylic acid, acrylonitrile, methyl methacrylate or N, N- methylene-bisacrylamide, the initiator is ammonium persulfate, mistake
Potassium sulfate or sodium hydrogensulfite.
CN104449617A discloses a kind of PAMA water-in-water emulsion water plugging profile control agent, it is described it is cloudy from
Sub- polyacrylamide water-in-water emulsion water plugging profile control agent is made up of PAMA water-in-water emulsion and crosslinking agent, is handed over
Connection agent accounts for the 30-150wt% of PAMA water-in-water emulsion, described PAMA water-in-water emulsion
Be water-soluble nonionic monomer, anionic monomer in the presence of inorganic salts, stabilizer, chelating agent, deionized water by initiator
Initiation is polymerized, and described crosslinking agent is the one or more in phenolic resin, chromium cross linker.
Although as described above, disclose a variety of profile control agents available for Petroleum finance field in the prior art,
Chromium compound is generally used in these profile control agents, which results in the environmental pollution in production process and post-processes burden,
And also need to be continued improved demand there is profile control effect.In addition, increasingly complexity and stone with oil well geological conditions
The increasingly reduction of oil recovery, equally there is urgent demand for new profile control agent.
Based on this consideration, a kind of profile control agent with premium properties and preparation method thereof how is developed, is exactly the current neck
Study hotspot and emphasis in domain, this has highly important industrial value and section for the technological progress of oil exploration and exploitation
Meaning is ground, and this basis that also exactly the present invention is accomplished is leaned on and power place.
The content of the invention
Based on disadvantages mentioned above, by concentrating on studies, the profile control agent in being produced for existing Oil/gas Well is showed the present inventor
Many defects out, by further investigation, after substantial amounts of creative work has been paid, so as to obtain a kind of novel oil production
With Chrome-free compound resin gel-like profile control agent and preparation method thereof and purposes, and then complete the present invention.
Specifically, technical scheme and content relate generally to following aspects.
One side, the present invention relates to a kind of oil recovery Chrome-free compound resin gel-like profile control agent, the profile control agent bag
Include nano-silicon dioxide modified cross-linked polymer, stabilizer, reinforcing agent, organic sulfonate, density adjuster, surfactant,
Auxiliary agent, thickener, wetting agent and water.
The present invention the oil recovery with Chrome-free compound resin gel-like profile control agent, in parts by weight, its concrete component
Content is as follows：
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, it is related to the " comprising " of composition, both wrapped
Contain open " comprising ", "comprising" etc. and its similar meaning, also contains enclosed " Consists of " etc. and its similar
Implication.
The present invention the oil recovery with Chrome-free compound resin gel-like profile control agent, the nano-silicon dioxide modified friendship
The parts by weight of linked polymer are 5-9 parts, such as can be 5 parts, 6 parts, 7 parts, 8 parts or 9 points.
Wherein, the nano-silicon dioxide modified cross-linked polymer is to be prepared by a method comprising the following steps
's：
A1：The preparation of pre-polymerization cross-linking agent solution, it comprises the following steps：
A1-1：Phenol and mass percent concentration are added in reactor for 37% formalin, are sufficiently stirred
Mixing, then heats to 70-75 DEG C, obtains reaction solution；
A1-2：Kaoline loaded base catalyst is added into reaction solution, and continues the stirring reaction at 70-75 DEG C
30-40 minutes, then naturally cool to room temperature and filter to isolate catalyst, filtrate is the pre-polymerization cross-linking agent solution；
A2：The anion-polyacrylamide that degree of hydrolysis is 15-17% and molecular weight is 1400-1600 ten thousand is added to
In ionized water, the anion-polyacrylamide aqueous solution that mass percentage concentration is 5-8% is configured to；
A3：At room temperature, modified manometer silicon dioxide micro mist is added into the anion-polyacrylamide aqueous solution, and
Under continuous stirring, the pre-polymerization cross-linking agent solution obtained in addition step A1 is added dropwise (i.e. to obtain in step A1-2 described
Pre-polymerization cross-linking agent solution), after addition, 50-60 DEG C, and stirring reaction 1-2 hours at such a temperature are warming up to, then by institute
Obtain reaction solution to pour into while hot in 20 DEG C of deionized water, divide and remove supernatant liquid, obtain spawn, i.e., described nanometer titanium dioxide
Si modification cross-linked polymer.
Wherein, in step A1-1, the mol ratio of phenol and the formaldehyde in formalin is 0.5-0.9:1, most preferably
For 0.75:1.
Wherein, in step A1-2, the kaoline loaded base catalyst is according to the method system comprised the following steps
：
B1：Kaolin is fully ground, 400-500 mesh sieves is crossed, obtains kaolin powder；
B2：The kaolin powder is calcined into 5-6 hours at 700-800 DEG C, room temperature is subsequently cooled to, after obtaining calcining
Powder；
B3：Powder is added in the NaOH aqueous solution that molar concentration is 3mol/L after this is calcined, and is warming up to 90 DEG C,
Reaction 2-3 hours are sufficiently stirred at this temperature, filtering, gained powder are fully washed 2-4 times with deionized water, it is last fully dry
It is dry, produce the kaoline loaded base catalyst.
Wherein, in step B3, the mass volume ratio of powder and the NaOH aqueous solution is 1 after the calcining:2-3g/ml, i.e.,
Powder is added in the 2-3ml NaOH aqueous solution after calcining described in per 1g.
Wherein, in step A1-2, the mass volume ratio of the kaoline loaded base catalyst and reaction solution is 1:
50-70g/ml, i.e., kaoline loaded base catalyst described in 1g is added into reaction solution described in every 50-70ml.
Wherein, in step A3, the modified manometer silicon dioxide micro mist is made according to the method comprised the following steps
's：
C1：The nano silicon that granularity is 5-15nm is fully dried into 2-4 hours at 150 DEG C, two after being dried
Silica；
C2：Silica after drying is added in absolute ethyl alcohol, is sufficiently stirred, then adds organo silane coupling agent,
And reaction 60-80 minutes are sufficiently stirred at 50-60 DEG C, obtain reaction solution；
C3：Reaction solution is centrifuged, obtained solid sequentially with benzene and absolute ethyl alcohol it is each fully washing 2-3 times, then
Vacuum drying, produces the modified manometer silicon dioxide micro mist.
Wherein, in step C2, the dosage of the absolute ethyl alcohol is not particularly limited, as long as can be convenient to react
Progress and post processing, those skilled in the art can carry out suitable selection and determine, no longer be described in detail herein.
Wherein, in step C2, the organo silane coupling agent is HMDS, γ-methacryloxy
Any one in propyl trimethoxy silicane or γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, most preferably γ-
(oxygen of 2,3- epoxies third) propyl trimethoxy silicane.
Wherein, in step C2, the mass ratio of silica and organo silane coupling agent is 1 after the drying:0.1-
0.14, such as can be 1:0.1、1:0.12 or 1:0.14.
Wherein, in step A3, the modified manometer silicon dioxide micro mist and the anion-polyacrylamide are water-soluble
The mass ratio of liquid is 1:10-30, such as can be 1:10、1:20 or 1:30.
Wherein, in step A3, the matter of the anion-polyacrylamide aqueous solution and the pre-polymerization cross-linking agent solution
It is 40-50 to measure ratio:1, such as can be 40:1、45:1 or 50:1.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the stabilizer are
0.1-0.16 parts, such as can be 0.1 part, 0.13 part or 0.16 part.
The stabilizer is Imarcaptoacetate dioctyltin, Bis(lauroyloxy)dioctyltin, the fourth of maleic acid two
Any one in tin or lower formula (I) compound,
Most preferably described (I) compound.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the reinforcing agent are
0.06-0.12 parts, such as can be 0.06 part, 0.08 part, 0.1 part or 0.12 part.
The reinforcing agent is Nonyl pheno (10) ether, Span-80, Laurate alcohol ester phenylacetate, polyoxyethylene polyoxy
Any one in propylene pentaerythrite ether or polypropylene glycerol aether, most preferably polyoxyethylene polyoxypropylene pentaerythrite
Ether.
The present invention the oil recovery with Chrome-free compound resin gel-like profile control agent, the parts by weight of the organic sulfonate
For 0.15-0.22 parts, such as it can be 0.15 part, 0.17 part, 0.19 part, 0.21 part or 0.22 part.
The organic sulfonate is any one in paratoluenesulfonic acid sodium salt, pyrovinic acid potassium or n-propyl sodium sulfonate.
The present invention the oil recovery with Chrome-free compound resin gel-like profile control agent, the parts by weight of the density adjuster
For 0.2-0.4 parts, such as it can be 0.2 part, 0.25 part, 0.3 part, 0.35 part or 0.4 part.
The density adjuster is ethylenediamine tetra-acetic acid or D-sorbite.
The present invention the oil recovery with Chrome-free compound resin gel-like profile control agent, the parts by weight of the surfactant
For 0.2-0.3 parts, such as it can be 0.2 part, 0.25 part or 0.3 part.
The surfactant is Fatty alcohol polyoxyethylene polyoxypropylene ether, structural formula R1O(C2H4O)p(C3H6O)qH,
Wherein R1For C10-C18Straight or branched alkyl, integers of the p between 4-8, integers of the q between 4-8.
Such surfactant is very known compound, can be commercially available by a variety of commercial channel, herein not
It is described in detail again.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the auxiliary agent are
0.05-0.1 parts, such as can be 0.05 part, 0.07 part, 0.09 part or 0.1 part.
The auxiliary agent is aluminium citrate.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the thickener are
0.1-0.2 parts, such as can be 0.1 part, 0.15 part or 0.2 part.
The thickener is that mass ratio is 1:2 sodium alginate and the mixture of 2- acrylamido -2- methyl propane sulfonic acids.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the wetting agent are
0.08-0.14 parts, such as can be 0.08 part, 0.1 part, 0.12 part or 0.14 part.
The wetting agent is sodium carboxymethylcellulose, sodium hydroxyethlcellulose or xanthans.
In the oil recovery of the invention with Chrome-free compound resin gel-like profile control agent, the parts by weight of the water are 30-40
Part, such as can be 30 parts, 35 parts or 40 parts.
As described above, the invention provides a kind of oil recovery Chrome-free compound resin gel-like profile control agent, the profile control agent leads to
The selection of suitable ingredients, and the modification of some components are crossed, so as to have a variety of excellent oil recovery effects, can be applicable to oil
Exploitation and Exploration Domain, have a good application prospect and industrial production potential.
Second aspect, the preparation method the invention further relates to above-mentioned oil recovery with Chrome-free compound resin gel-like profile control agent,
Methods described comprises the following steps：
S1：The nano-silicon dioxide modified cross-linked polymer of respective parts by weight, stabilizer, reinforcing agent, organic is weighed respectively
Sulfonate, density adjuster, surfactant, auxiliary agent, thickener, wetting agent and water.；
S2：Xiang Shuizhong is followed successively by total dosage 80-90% nano-silicon dioxide modified cross-linked polymer, stabilizer, enhancing
Agent, organic sulfonate, density adjuster and surfactant, and 40-50 DEG C is warming up to, it is sufficiently stirred, until as uniformly viscous
Property liquid；
S3：The 10-20% of auxiliary agent, thickener, wetting agent and surplus nanometer is added into the homogeneous viscous liquid
Silica modified cross-linked polymer, continue to stir 30-50 minutes, obtain homogeneous viscous liquid, be that the described of the present invention is adopted
Oil uses Chrome-free compound resin gel-like profile control agent.
The preparation method of the present invention, by suitable preparation process, especially nano-silicon dioxide modified crosslinking is poly-
The addition in batches of compound, can obtain that stability is good and the purpose product of other excellent effects.
3rd aspect, the present invention relates to above-mentioned oil recovery with Chrome-free compound resin gel-like profile control agent in oil exploitation
Purposes.
Inventor has found that the oil recovery Chrome-free compound resin gel-like profile control agent has a variety of excellent effects, such as stable
Property good, high temperature tolerance, high resistance to salinity and other effects, and the environmental protection of each composition, safety, to environment nonhazardous or negative effect,
It can be used to realize various profile control effects, had a good application prospect in industrialization and productive potentialities.
As described above, the invention provides a kind of oil recovery with Chrome-free compound resin gel-like profile control agent and preparation method thereof and
Purposes, the profile control agent is modified etc. by the selection of suitable ingredients and/work, and by specific preparation method, so as to have
A variety of superperformances, there is good industrialization potential in energy development field.
Brief description of the drawings
Accompanying drawing 1 is spawn (the i.e. nano-silicon dioxide modified cross-linked polymer obtained by preparation example 1 of the present invention
JHW electron microscope).
Embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not forms any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
React example 1：The preparation of kaoline loaded base catalyst
B1：Kaolin is fully ground, 400-500 mesh sieves is crossed, obtains kaolin powder；
B2：The kaolin powder is calcined 5.5 hours at 750 DEG C, is subsequently cooled to room temperature, powder after being calcined
End；
B3：Powder is added in the NaOH aqueous solution that molar concentration is 3mol/L after this is calcined, and is warming up to 90 DEG C,
Reaction 2.5 hours is sufficiently stirred at this temperature, filtering, gained powder is fully washed 2-4 times with deionized water, it is last fully dry
It is dry, kaoline loaded base catalyst is produced, is named as CAT.
Wherein, in step B3, the mass volume ratio of powder and the NaOH aqueous solution is 1 after the calcining:2.5g/ml.
React example 1-1：The preparation of kaoline loaded base catalyst
In addition to step B2 is dispensed, i.e., step B1 kaolin powder is directly carried out to step B3 reaction, other operations
It is constant, so as to which reaction example 1 be repeated, preparation example 1-1 is obtained, obtained kaoline loaded base catalyst is named as
DCAT。
React example 2：The preparation of modified manometer silicon dioxide micro mist
C1：The nano silicon that granularity is 5-15nm is fully dried 3 hours at 150 DEG C, dioxy after being dried
SiClx；
C2：Silica after drying is added in appropriate absolute ethyl alcohol, is sufficiently stirred, it is even then to add organic machine silane
Join agent γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, and reaction 70 minutes is sufficiently stirred at 55 DEG C, reacted
Liquid；
C3：Reaction solution is centrifuged, obtained solid sequentially with benzene and absolute ethyl alcohol it is each fully washing 2-3 times, then
Vacuum drying, obtains modified manometer silicon dioxide micro mist, is named as WF.
Wherein, in step C2, the mass ratio of silica and organo silane coupling agent is 1 after the drying:0.12.
React example 2-1-2-2：The preparation of nanometer titanium dioxide silicon powder
Except organic machine silane coupling agent γ-(oxygen of 2,3- epoxies third) the propyl trimethoxy silicon that will be reacted in the step C2 of example 2
Alkane replaces with outside HMDS and γ-methacryloxypropyl trimethoxy silane respectively, and other operations are not
Become, so as to which reaction example 2 be repeated, obtain reacting example 2-1 and react example 2-2, obtained modified manometer silicon dioxide is micro-
Powder is respectively designated as DWF1 and DWF2.
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 following steps：
A1-1：Phenol and mass percent concentration are added in reactor (phenol and first for 37% formalin
The mol ratio of formaldehyde in the aldehyde aqueous solution is 0.75:1), it is thoroughly mixed, then heats to 70 DEG C, obtain reaction solution；
A1-2：Kaoline loaded base catalyst CAT (the kaoline loaded base catalysts are added into reaction solution
The mass volume ratio of CAT and reaction solution is 1:60g/ml), and stirring reaction 35 minutes at 70 DEG C are continued, it is then naturally cold
But to room temperature and catalyst is filtered to isolate, filtrate is the pre-polymerization cross-linking agent solution；
A2：The anion-polyacrylamide that degree of hydrolysis is 15-17% and molecular weight is 15,000,000 is added to deionization
In water, the anion-polyacrylamide aqueous solution that mass percentage concentration is 7% is configured to；
A3：At room temperature, modified manometer silicon dioxide micro mist WF is added into the anion-polyacrylamide aqueous solution
(mass ratio of the WF and the anion-polyacrylamide aqueous solution is 1:20), and under continuous stirring, it is added dropwise and adds
The pre-polymerization cross-linking agent solution (the anion-polyacrylamide aqueous solution and the pre- polyhydroxy crosslinking agent obtained in step A1
The mass ratio of solution is 45:1), after addition, 55 DEG C, and stirring reaction 1.5 hours at such a temperature are warming up to, then will
Gained reaction solution pours into 20 DEG C of deionized water while hot, divides and removes supernatant liquid, obtains spawn, as described nanometer two
Silica modified cross-linked polymer, is named as JHW.
Obtained it can be seen from the JHW electron microscopes of accompanying drawing 1 for chain polyacrylamide gel class material, inside it
Substantial amounts of nano-silicon dioxide particle (stain therein) has been coupled, by so handling, has significantly enhanced gel strength,
So as to 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：In addition to the catalyst in step A1-2 is replaced with into DCAT by CAT, other operations are constant, so as to
Preparation example 1 is repeated, obtains preparation example 1-1, obtained nano-silicon dioxide modified cross-linked polymer is named as
DJHW1。
Preparation example 1-2-1-3：Except by the modified manometer silicon dioxide micro mist WF in step A3 replace with respectively DWF1 and
Outside DWF2, other operations are constant, so as to which preparation example 1 be repeated, preparation example 1-2 and preparation example 1-3 obtained, by what is obtained
Nano-silicon dioxide modified cross-linked polymer is respectively designated as DJHW2 and DJHW3.
Preparation example 1-4：Except the modified manometer silicon dioxide micro mist WF in step A3 is replaced with into nano silicon respectively
(it is the nano silicon that granularity is 5-15nm, and does not carry out the step C1-C3 of present invention modification) outside, it is other
Operation is constant, so as to which preparation example 1 be repeated, obtains preparation example 1-2 and preparation example 1-3, the nanometer titanium dioxide that will be obtained
Si modification cross-linked polymer is named as DJHW4.
It should be noted that in examples below, each component used in step S2-S3 is institute in step S1
The corresponding each component weighed.
Embodiment 1：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
S1：The nano-silicon dioxide modified cross-linked polymer JHW of 5 parts by weight is weighed respectively, formula described in 0.1 parts by weight stabilizer
(I) compound, 0.06 parts by weight reinforcing agent polyoxyethylene polyoxypropylene pentaerythrite ether, 0.15 parts by weight organic sulfonate are to first
Benzene sulfonic acid sodium salt, 0.2 parts by weight density adjuster ethylenediamine tetra-acetic acid, 0.2 parts surfactant C12H25O(C2H4O)4
(C3H6O)6H (wherein C12H25For dodecyl), 0.05 parts by weight auxiliary agent aluminium citrate, 0.1 parts by weight of thickening agent is (for quality
Than for 1:2 sodium alginate and the mixture of 2- acrylamido -2- methyl propane sulfonic acids), 0.08 parts by weight wetting agent carboxymethyl
Sodium cellulosate and 30 parts by weight water；
S2：Xiang Shuizhong is followed successively by the nano-silicon dioxide modified cross-linked polymer (i.e. 4 parts by weight) of total dosage 80%, whole
Stabilizer, whole reinforcing agents, whole organic sulfonates, the surfactant of whole density adjusters and whole, and
40 DEG C are warming up to, is sufficiently stirred, until turning into homogeneous viscous liquid；
S3：Whole auxiliary agents, whole thickeners, whole wetting agents and residue are added into the homogeneous viscous liquid
The 20% nano-silicon dioxide modified cross-linked polymer (i.e. 1 parts by weight) of amount, continue stirring 30 minutes, obtain homogeneous viscous liquid
Body, oil recovery Chrome-free compound resin gel-like profile control agent is produced, is named as TPL1.
Embodiment 2：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
S1：The nano-silicon dioxide modified cross-linked polymer JHW of 7 parts by weight is weighed respectively, described in 0.16 parts by weight stabilizer
Formula (I) compound, 0.09 parts by weight reinforcing agent polyoxyethylene polyoxypropylene pentaerythrite ether, 0.18 parts by weight organic sulfonate first
Base potassium sulfonate, 0.4 parts by weight density adjuster D-sorbite, 0.3 parts surfactant C16H33O(C2H4O)6(C3H6O)8H
(wherein C16H33For n-hexadecyl), 0.07 parts by weight auxiliary agent aluminium citrate, 0.15 parts by weight of thickening agent (be 1 for mass ratio:2
Sodium alginate and 2- acrylamido -2- methyl propane sulfonic acids mixture), 0.14 parts by weight wetting agent sodium hydroxyethlcellulose
With 35 parts by weight water；
S2：Xiang Shuizhong is followed successively by the nano-silicon dioxide modified cross-linked polymer (i.e. 6.3 parts by weight), complete of total dosage 90%
The stabilizer in portion, whole reinforcing agents, whole organic sulfonates, whole density adjusters and whole surfactants,
And 45 DEG C are warming up to, it is sufficiently stirred, until turning into homogeneous viscous liquid；
S3：Whole auxiliary agents, whole thickeners, whole wetting agents and residue are added into the homogeneous viscous liquid
The 10% nano-silicon dioxide modified cross-linked polymer (i.e. 0.7 parts by weight) of amount, continue stirring 40 minutes, obtain homogeneous viscous
Liquid, oil recovery Chrome-free compound resin gel-like profile control agent is produced, is named as TPL2.
Embodiment 3：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
S1：The nano-silicon dioxide modified cross-linked polymer JHW of 9 parts by weight is weighed respectively, described in 0.13 parts by weight stabilizer
Formula (I) compound, 0.12 parts by weight reinforcing agent polyoxyethylene polyoxypropylene pentaerythrite ether, 0.22 parts by weight organic sulfonate are just
Propyl sulfonic acid sodium, 0.3 parts by weight density adjuster ethylenediamine tetra-acetic acid, 0.25 parts surfactant C18H37O(C2H4O)8
(C3H6O)4H (wherein C18H37For n-octadecane base), 0.1 parts by weight auxiliary agent aluminium citrate, 0.2 parts by weight of thickening agent is (for quality
Than for 1:2 sodium alginate and the mixture of 2- acrylamido -2- methyl propane sulfonic acids), 0.11 parts by weight wetting agent xanthans
With 40 parts by weight water；
S2：Xiang Shuizhong be followed successively by total dosage 85% nano-silicon dioxide modified cross-linked polymer (i.e. 7.65 parts by weight),
Whole stabilizer, whole reinforcing agents, whole organic sulfonates, whole density adjusters and whole surface-actives
Agent, and 50 DEG C are warming up to, it is sufficiently stirred, until turning into homogeneous viscous liquid；
S3：Whole auxiliary agents, whole thickeners, whole wetting agents and residue are added into the homogeneous viscous liquid
The 15% nano-silicon dioxide modified cross-linked polymer (i.e. 1.35 parts by weight) of amount, continue stirring 50 minutes, uniformly glued
Property liquid, produces oil recovery Chrome-free compound resin gel-like profile control agent, is named as TPL3.
Embodiment 4-7：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
In addition to the DJHW1-DJHW4 for using preparation example 1-1-1-4 respectively replaces the JHW in embodiment 1-3, other operations
It is constant, so as to be carried out a 4-7, used nano-silicon dioxide modified friendship according to embodiment 1-3 method respectively
Linked polymer (abbreviation cross-linked polymer), embodiment corresponding relation and gained recover the oil with Chrome-free compound resin gel-like profile control agent
Name as shown in the table.
Embodiment 8-10：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
In addition to formula (I) compound in embodiment 1-3 is replaced using following stabilizer respectively, other operations are constant,
So as to be carried out a 8-10, used stabilizer, embodiment corresponding relation and institute according to embodiment 1-3 method respectively
It must recover the oil as shown in the table with the name of Chrome-free compound resin gel-like profile control agent.
Embodiment 11-14：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
In addition to the polyoxyethylene polyoxypropylene pentaerythrite ether in embodiment 1-3 is replaced using following reinforcing agent respectively,
Other operations are constant, so as to be carried out a 11-14, used reinforcing agent, reality according to embodiment 1-3 method respectively
The name for applying a corresponding relation and gained oil recovery Chrome-free compound resin gel-like profile control agent is as shown in the table.
Embodiment 15-20：The preparation recovered the oil with Chrome-free compound resin gel-like profile control agent
Embodiment 15-17：In addition to all nano-silicon dioxide modified cross-linked polymers are added in step s 2 entirely (i.e.
Do not added in step S3), other operations are constant, so as to which embodiment 1-3 be repeated, obtain embodiment 15-17, will obtain
Oil recovery be sequentially named as TPJ15, TPJ16 and TPJ17 with Chrome-free compound resin gel-like profile control agent.
Embodiment 18-20：In addition to all nano-silicon dioxide modified cross-linked polymers are added in step s3 entirely (i.e.
Do not added in step S2), other operations are constant, so as to which embodiment 1-3 be repeated, obtain embodiment 18-20, will obtain
Oil recovery be sequentially named as TPJ18, TPJ19 and TPJ20 with Chrome-free compound resin gel-like profile control agent.
Performance test
The performance test of different indexs is carried out to each profile control agent as follows, it is specific as follows.
1st, the investigation of sealing characteristics
The test process comprises the following steps that：Carried out using simulation fill out sand tube, first by multiple fill out sand tube at room temperature
Its permeability is measured, then the at the uniform velocity different profile control agents of the pressure injection present invention are (relative to every cm of fill out sand tube2Sectional area and
Speech, injection rate are 0.2ml/ minutes, and pressure 0.1MPa, injection length is 6 hours)；After injection terminates, in the same way
The permeability of fill out sand tube is measured again, and the profile control agent can be calculated according to the permeability before the injection of fill out sand tube and after injection
Sealing ratiod (permeability × 100% before sealing ratiod (%)=(permeability after permeability-injection before injection)/injection), concrete outcome
It see the table below：
As seen from the above table：1st, in the preparation method of nano-silicon dioxide modified cross-linked polymer, when the catalyst used
In kaolin when not calcined, causing the plugging effect of final products to have substantially reduces (see TPJ4 data), and this proves to work as
When being calcined to kaolin, the catalytic effect of gained catalyst can be strengthened, so as to improve gained pre-polymerization cross-linking agent solution
With anion-polyacrylamide and the reaction effect of modified manometer silicon dioxide micro mist；2nd, from TPJ5-TPJ6 data,
Organo silane coupling agent used in modified manometer silicon dioxide micro mist preparation method has significant shadow for final result
Ring, wherein γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane has best effect, and other organo silane coupling agents are led
Cause sealing ratiod to be greatly lowered, reason be the failure to be completely contained in chain polyacrylamide gel class material (and use γ-
Then largely it is included in during (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, sees accompanying drawing 1), so as to cause final gel
Intensity has obvious reduction, so causes extension over time and final sealing characteristics reduces；3 and when fine silica powder not
(see TPJ7) when modified, sealing characteristics reduction is the most obvious, or even has lost application foundation；4th, from TPJ8-TPJ14 number
According to visible, stabilizer is most preferably that formula (I) compound, reinforcing agent are most preferably polyoxyethylene polyoxypropylene pentaerythrite ether, its
Its stabilizer and reinforcing agent cause sealing characteristics to decrease；5 and from TPJ15-TPJ20, when in step S2 or S3
It is disposable that sealing characteristics is also obvious to be reduced when adding all nano-silicon dioxide modified cross-linked polymers, this prove when point
When adding twice, enable to have more thoroughly reaction and/or interaction between each component, it is optimal so as to achieve
Different plugging effect.
2nd, the investigation of resistance to salinity
Complex mineral salt solution is prepared, wherein the mass percent concentration of various components is as follows：NaCl is 10%, KCl is
5.5%th, MgCl2For 1.5%, CaCl2For 1%, ZnCl2For 1.25% and AlCl3For 1.4%.
The profile control agent of the present invention is added in isometric above-mentioned complex mineral salt solution, is sufficiently stirred, until having mixed
Entirely, after standing 10 days, its sealing characteristics is measured according still further to above-mentioned identical method, as a result see the table below：
As can be seen here, profile control agent TPJ1-TPJ3 of the invention has good resistance to salinity, even so high mineralising
Under degree, still there is 96.7-97.4% high sealing ratiod after 10 days.And the change of other components, change of preparation method etc. are led
Sealing ratiod is caused to have obvious reduction (and reduction amplitude is bigger).
3rd, the investigation of resistance to elevated temperatures
By the profile control agent of the present invention in high pressure sealing tank is encased in, heat rolling 24 hours at a high temperature of 160 DEG C；Terminate
Afterwards, room temperature is naturally cooled to, then according to the same procedure in above-mentioned the investigation of sealing characteristics " 1, ", after testing its high-temperature process
Sealing characteristics.As a result see the table below.
As can be seen here, profile control agent TPJ1-TPJ3 of the invention has good resistance to elevated temperatures, after heat rolling 24 hours,
Still there is the sealing ratiod higher than 97%, and TPJ4-TPJ20 has the TPJ8- that significant reduction, especially stabilizer change
TPJ10 reduces amplitude maximum, this demonstrate that the type of stabilizer can significantly affect resistance to elevated temperatures.
4th, alkaline-resisting investigation
Secure ph is the 12.0 NaOH aqueous solution, and obtained profile control agent in above-mentioned the investigation of sealing characteristics " 1, " is added
Into isometric NaOH aqueous solution, it is sufficiently stirred, until mixing is complete, after standing 8 days, it is measured according still further to identical method
Sealing characteristics, as a result it see the table below：
As can be seen here, profile control agent TPJ1-TPJ3 of the invention has good alkaline resistance properties, and 12% is up in pH value
After standing 8 days in NaOH aqueous slkalis, still there is the sealing ratiod higher than 96%, and TPJ4-TPJ20 has significant reduction.
5th, the investigation of tensile strength and elongation at break
JHW, DJHW1-DJHW4 obtained above gel strength are investigated, it is specific as follows：Above-mentioned preparation example is obtained respectively
Gel JHW, DJHW1-DJHW4 0.5cm × 0.5cm × 0.2cm thin slice is made, then dried 30 minutes at 80 DEG C；
Dry and be attached to after terminating on stretching measuring instrument, stretched with the speed of 15cm/ minutes, untill breaking, so as to investigate
Its tensile strength and elongation at break, concrete outcome see the table below.
As can be seen here, profile control agent TPJ1-TPJ3 of the invention has very excellent tensile strength and elongation at break；And
DJHW1 has obvious reduction in the two indexs；And the DJHW2-DJHW3 for changing organo silane coupling agent refers at the two
Put on reduce it is more notable, this again demonstrate the importance of organo silane coupling agent species.It is significantly more to be, DJHW4 drops
Low amplitude is maximum, this demonstrate that carrying out so being modified can use to obtain unexpected technique effect to nano silicon.
As described above, the invention provides a kind of oil recovery with Chrome-free compound resin gel-like profile control agent and preparation method thereof and
Purposes in the fields such as oily exploitation, drilling well, the profile control agent pass through unique modification to raw material, appropriately selected, the preparation of component
The distinct steps of method and the synergy of technological parameter etc., so as to achieve the purpose product with best effects, have
Excellent mechanical performance, heat resistance, resistance to salinity and alkaline resistance properties etc., have a good application prospect in energy extraction field
And industrialization potential.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to the protection model of the limitation present invention
Enclose.In addition, it should also be understood that, after the technology contents of the present invention have been read, those skilled in the art can make each to the present invention
Kind change, modification and/or variation, all these equivalent form of values equally fall within the guarantor that the application appended claims are limited
Within the scope of shield.
Claims (3)
1. one kind is recovered the oil and uses Chrome-free compound resin gel-like profile control agent, it is characterised in that：The profile control agent includes nanometer titanium dioxide
Si modification cross-linked polymer, stabilizer, reinforcing agent, organic sulfonate, density adjuster, surfactant, auxiliary agent, thickener,
Wetting agent and water；
In parts by weight, the concrete component content of the profile control agent is as follows：
The nano-silicon dioxide modified cross-linked polymer is prepared by a method comprising the following steps：
A1：The preparation of pre-polymerization cross-linking agent solution, it comprises the following steps：
A1-1：Phenol and mass percent concentration are added in reactor for 37% formalin, are thoroughly mixed,
70-75 DEG C is then heated to, obtains reaction solution；
A1-2：Kaoline loaded base catalyst is added into reaction solution, and continues the stirring reaction 30-40 at 70-75 DEG C
Minute, then naturally cool to room temperature and filter to isolate catalyst, filtrate is the pre-polymerization cross-linking agent solution；
A2：The anion-polyacrylamide that degree of hydrolysis is 15-17% and molecular weight is 1400-1600 ten thousand is added to deionization
In water, the anion-polyacrylamide aqueous solution that mass percentage concentration is 5-8% is configured to；
A3：At room temperature, modified manometer silicon dioxide micro mist is added into the anion-polyacrylamide aqueous solution, and is being held
Under continuous stirring, the pre-polymerization cross-linking agent solution for adding in step A1 and obtaining is added dropwise, after addition, is warming up to 50-60 DEG C, and
Stirring reaction 1-2 hours at such a temperature, then gained reaction solution is poured into while hot in 20 DEG C of deionized water, divide and go upper liquid
Body, spawn is obtained, i.e., described nano-silicon dioxide modified cross-linked polymer；
The kaoline loaded base catalyst is according to made from the method comprised the following steps：
B1：Kaolin is fully ground, 400-500 mesh sieves is crossed, obtains kaolin powder；
B2：The kaolin powder is calcined into 5-6 hours at 700-800 DEG C, is subsequently cooled to room temperature, powder after being calcined
End；
B3：Powder is added in the NaOH aqueous solution that molar concentration is 3mol/L after this is calcined, and is warming up to 90 DEG C, in the temperature
Reaction 2-3 hours are sufficiently stirred under degree, filtering, gained powder are fully washed 2-4 times with deionized water, it is last fully to dry,
Produce the kaoline loaded base catalyst；
Wherein, the modified manometer silicon dioxide micro mist is according to made from the method comprised the following steps：
C1：The nano silicon that granularity is 5-15nm is fully dried into 2-4 hours, titanium dioxide after being dried at 150 DEG C
Silicon；
C2：Silica after drying is added in absolute ethyl alcohol, is sufficiently stirred, then adds organo silane coupling agent, and
Reaction 60-80 minutes are sufficiently stirred at 50-60 DEG C, obtain reaction solution；
C3：Reaction solution is centrifuged, obtained solid is sequentially with each fully washing of benzene and absolute ethyl alcohol 2-3 times, then vacuum
Dry, produce the modified manometer silicon dioxide micro mist；
The stabilizer is lower formula (I) compound,
The reinforcing agent is polyoxyethylene polyoxypropylene pentaerythrite ether；
The auxiliary agent is aluminium citrate.
2. the preparation method recovered the oil described in claim 1 with Chrome-free compound resin gel-like profile control agent, methods described includes as follows
Step：
S1：Nano-silicon dioxide modified cross-linked polymer, stabilizer, reinforcing agent, the organic sulfonic acid of respective parts by weight are weighed respectively
Salt, density adjuster, surfactant, auxiliary agent, thickener, wetting agent and water；
S2：Xiang Shuizhong is followed successively by total dosage 80-90% nano-silicon dioxide modified cross-linked polymer, stabilizer, reinforcing agent, had
Machine sulfonate, density adjuster and surfactant, and 40-50 DEG C is warming up to, it is sufficiently stirred, until turning into homogeneous viscous liquid
Body；
S3：The 10-20% of auxiliary agent, thickener, wetting agent and surplus nano-silica is added into the homogeneous viscous liquid
SiClx modified cross-linked polymers, continue to stir 30-50 minutes, obtain homogeneous viscous liquid, as described oil recovery Chrome-free is compound
Resin gel class profile control agent.
3. purposes of the oil recovery according to claim 1 with Chrome-free compound resin gel-like profile control agent in oil exploitation.
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| CN106800921B (en) * | 2016-12-02 | 2019-06-07 | 长江大学 | The stifled frozen glue of wide temperature high salinity tune |
| CN110699056A (en) * | 2018-07-09 | 2020-01-17 | 中国石油天然气股份有限公司 | Steam channeling sealing agent |
| CN111088021B (en) * | 2018-10-24 | 2022-01-28 | 中国石油化工股份有限公司 | Low-density gel particle profile control and flooding agent and preparation method thereof |
| 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 |
| CN114456783A (en) * | 2022-01-14 | 2022-05-10 | 西南石油大学 | Inorganic-organic composite profile control water shutoff agent and using method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5257664A (en) * | 1990-12-03 | 1993-11-02 | Mobil Oil Corporation | Steam injection profile control agent and process |
| CN102485830A (en) * | 2010-12-02 | 2012-06-06 | 北京化工大学 | Profile control oil-displacement agent for core-shell type inorganic/organic polymer composite microballoon |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
-
2015
- 2015-10-15 CN CN201510665156.6A patent/CN105368423B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5257664A (en) * | 1990-12-03 | 1993-11-02 | Mobil Oil Corporation | Steam injection profile control agent and process |
| CN102485830A (en) * | 2010-12-02 | 2012-06-06 | 北京化工大学 | Profile control oil-displacement agent for core-shell type inorganic/organic polymer composite microballoon |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
Non-Patent Citations (1)
| Title |
|---|
| AM-EHA共聚物/SiO2复合调剖剂的研究;刘宝军;《中国优秀硕士学位论文全文数据库工程科技I辑》;20140415;B019-18 * |
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