CN102965088A - Environment-friendly crosslinking and gelling retarding profile control agent and preparation method thereof - Google Patents
Environment-friendly crosslinking and gelling retarding profile control agent and preparation method thereof Download PDFInfo
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- CN102965088A CN102965088A CN2012104692534A CN201210469253A CN102965088A CN 102965088 A CN102965088 A CN 102965088A CN 2012104692534 A CN2012104692534 A CN 2012104692534A CN 201210469253 A CN201210469253 A CN 201210469253A CN 102965088 A CN102965088 A CN 102965088A
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Abstract
The invention discloses an environment-friendly crosslinking and gelling retarding profile control agent and a preparation method thereof and belongs to the field of enhanced oil recovery technologies for oilfields. The profile control agent comprises a primary agent, i.e. hydrophobic association, a crosslinking agent, i.e. aluminum citrate, an antioxidant, i.e. sodium sulfite, and a retarding agent, i.e. sodium malate, and contains all the ingredients in percentage by weight: 0.1-0.4% of hydrophobic association, 0.01-0.02% of aluminum citrate, 0.015-0.025% of sodium sulfite, 0.005-0.020% of sodium malate and the balance of water. The profile control agent disclosed by the invention has the characteristics that the profile control agent is environment-friendly and is free of damage/injury to environments/human bodies; the crosslinking is retarded, and the gelling time is prolonged, thereby being beneficial to high-dose injection and deep profile control; the plugging rate is high; and the profile control agent has certain temperature-resistant and salt-tolerant performance and scouring resistance. The profile control agent can be used for adjusting a water absorption profile of a water-flood well and improving the water-flood development effect of oilfields.
Description
Technical field
The present invention relates to the ﹠ Application on Oil Recovery field, particularly a kind of environmental protection delayed cross-linking gel profile control agent and preparation method thereof.
Background technology
China's most of Oilfield using waterflooding mode to replenish the underground deficit because being caused after the crude oil extraction, keeps or improves the pressure of oil reservoir simultaneously, realizes the high and stable yields of crude oil.In the waterflooding process, the nonuniformity of oil reservoir can cause the injected water individual layer to be advanced by leaps and bounds or the plane tonguing; The macropore that long-term souring forms can cause injected water along macropore channelling, low permeability layer suction deficiency or inhale less than water, reduces widely the effect of water flooding.
In order to improve intake profile, improve the waterflooding development effect in oil field, Chinese scholars has been developed polytype amendment.At present, polymer gel class amendment is used more in desk research and field test.The linking agent system that polymer gel class amendment adopts is mainly organic phenolic aldehyde cross-linking system and Cr (III) cross-linking system, adopts the gel profile control agent of this two classes linking agent preparation all can obtain preferably effect in desk research and test in place.The Rainbow Ranch Oilfield using gel in U.S. Wyoming State Campbell county carries out profile control, and the profile control system is comprised of chromium acetate and polyacrylamide, is divided into 3 slug injection profile agent 9540m
3, the water injection pressure ascensional range after the construction is 6.89MPa, the accumulative total oil increment reaches 2385m
3(Gu Xikui. the chemical deep transfer drive state of the art and progress [J]. petrochemical complex is used, and 2009,28 (3): 4-7.).Xinjiang Oilfield adopts phenolic aldehyde cross linked gel amendment that 9K1h oil reservoir 7 well groups in land are carried out profile control, corresponding oil well during behind the profile control 2nd month to 6th month, seen obvious oil increasing effect (Chen Lunjun. the hydrophobic associated polymer gel profile control agent is in the application [J] of land 9K1h oil reservoir. Southwest Petrol University's journal natural science edition, 2009,31 (4): 134-136.).
The basal component of organic phenolic crosslinkers system is phenol and formaldehyde, and this class linking agent is mainly used in the deep profile controlling of high-temperature oil reservoir, but toxicity is large, has irritating smell.Cr (III) linking agent is the very strong cross-linking system of a kind of adaptability, it goes for wide temperature range and pH value, gelation time is controlled, reactive behavior is stronger, intensity behind the one-tenth glue is larger, and stability is better, but has larger toxicity with the gel profile control agent of Cr (III) linking agent preparation, easily environment is damaged, also can damage workmen's health.
Adopt the Tiorco 677 linking agent can avoid phenol, formaldehyde, heavy metal to the injury of environment and human body.Low temperature, acidity or neutral reservoir condition during Al (III) cross-linking system is fit to, toxicity is very little.But the gelation time that a deficiency that adopts Al (III) cross-linking system to prepare gel profile control agent is exactly gel is too short, in polymers soln, add fast accelerated gum behind Al (III) cross-linking system, badly influence like this injection efficiency of gel profile control agent and the performance of deep transfer drive.
Therefore, develop a kind of environmental protection delayed cross-linking gel profile control agent to improving the intake profile of water injection well, enlarge the swept volume of injected water, it is significant to improve the water flooding effect.
Summary of the invention
The objective of the invention is: provide a kind of to environment and human body do not have injury, can delayed cross-linking gel profile control agent.
The present invention is that the technical scheme that its technical problem of solution is taked is:
One, the feed composition weight ratio of environmental protection delayed cross-linking gel profile control agent:
1, host hydrophobic associated polymer: 0.1%～0.4%;
2, linking agent Tiorco 677: 0.01%～0.02%;
3, antioxidant S-WAT: 0.015%～0.025%;
4, retardant sodium malate: 0.005%～0.020%;
5, all the other are water.
The molecular weight of described hydrophobic associated polymer is 8 * 10
6
Two, the preparation method of environmental protection delayed cross-linking gel profile control agent
The hydrophobic associated polymer mother liquor of preparation 0.5%, stand-by behind the placement 24h; Prepare respectively 1.0% aluminum citrate solution, sodium sulfite solution and sodium malate solution; In wide-necked bottle, add successively a certain amount of hydrophobic associated polymer mother liquor, aluminum citrate solution, sodium sulfite solution, sodium malate solution and water; Wide-necked bottle is placed on stirs 15min on the magnetic stirring apparatus, prepare environmental protection delayed cross-linking gel profile control agent.
Using method of the present invention is: prepare environmental protection delayed cross-linking gel profile control agent by the feed composition weight percent; A certain amount of environmental protection delayed cross-linking gel profile control agent is clamp-oned from well; With clear water (on-the-spot injected water) environmental protection delayed cross-linking gel profile control agent is replaced into the stratum; Behind closing well 24～72h, normal water filling drives a well.
The invention has the beneficial effects as follows: the environmental protection delayed cross-linking gel profile control agent that the present invention uses is formulated by hydrophobic associated polymer, linking agent Tiorco 677, antioxidant S-WAT and retardant sodium malate, and the gel profile control agent of formation does not damage environment and human body; Can delayed cross-linking, prolong gelation time, be conducive to heavy dose of the injection and the deep transfer drive; Sealing ratiod is high; The heat-resistant salt-resistant better performances; Has simultaneously certain resistance to erosion ability.This amendment can be used for adjusting profile-log of water injection, enlarges the injected water swept volume, improves the water flooding effect.
Description of drawings
Fig. 1 is the microtexture of environmental protection delayed cross-linking gel profile control agent under the scanning electron microscope;
Fig. 2 is that the retardant dosage is to the influence curve of environmental protection delayed cross-linking gel profile control agent gelation time;
Fig. 3 is the heatproof curve of environmental protection delayed cross-linking gel profile control agent;
Fig. 4 is the salt tolerant curve of environmental protection delayed cross-linking gel profile control agent;
Fig. 5 is the flow performance curve of environmental protection delayed cross-linking gel profile control agent.
Embodiment
Below by embodiment the present invention is further specified.
Embodiment 1: the microtexture of environmental protection delayed cross-linking gel profile control agent under the scanning electron microscope
With the hydrophobic associated polymer mother liquor of preparation water (ion content of preparation water sees Table 1) preparation 0.5%, the fully rear 24h that places of stirring and dissolving; Prepare respectively 1.0% Tiorco 677,1.0% S-WAT and 1.0% sodium malate solution with distilled water; Add 0.5% hydrophobic associated polymer mother liquor 60ml, 1.0% Tiorco 677 1.5ml, 1.0% S-WAT 2.0ml, 1.0% sodium malate 1.6ml and 34.9ml preparation water in the 200ml wide-necked bottle, wide-necked bottle is placed on stirs 30min on the magnetic stirring apparatus, make environmental protection delayed cross-linking gel profile control agent; Again wide-necked bottle is placed in the thermostat container that temperature setting is set to 65 ℃ and becomes glue; Microtexture with scanning electron microscopic observation environmental protection delayed cross-linking gel profile control agent, experimental result as shown in Figure 1, Existential Space tridimensional network in the environmental protection delayed cross-linking gel profile control agent, this structure are conducive to strengthen gelling strength and the heat-resistant salt-resistant performance of environmental protection delayed cross-linking gel profile control agent.
The ion content of table 1 preparation water
Embodiment 2: the retardant dosage is on the impact of environmental protection delayed cross-linking gel profile control agent gelation time
Method according to preparation environmental protection delayed cross-linking gel profile control agent among the embodiment 1, the fixing dosage of hydrophobic associated polymer (0.3%), linking agent Tiorco 677 (0.015%), antioxidant S-WAT (0.020%), change the dosage of retardant sodium malate (0.006%, 0.008%, 0.010%, 0.012%, 0.014%, 0.016%, 0.018%, 0.020%), make the environmental protection delayed cross-linking gel profile control agent that contains different dosage retardant sodium malates.The wide-necked bottle that environmental protection delayed cross-linking gel profile control agent is housed is placed in the thermostat container that temperature setting is set to 65 ℃ becomes glue, regularly use Brookfield DV-III rotational viscosimeter (65 ℃ of temperature, shearing rate 7.34s
-1) measure the gelation time of environmental protection delayed cross-linking gel profile control agent.Experimental result as shown in Figure 2, the amendment gelation time that does not add the retardant sodium malate is 4.0h, after adding the retardant sodium malate, the gelation time of amendment all prolongs to some extent, the retardant sodium malate gelation time of adding 0.020% extends to 24.2h, illustrate that the retardant sodium malate can make amendment have the performance of delayed cross-linking, be conducive to realize heavy dose of the injection and the deep transfer drive.
Embodiment 3: the heat resistance of environmental protection delayed cross-linking gel profile control agent
According to the method for preparation environmental protection delayed cross-linking gel profile control agent among the embodiment 1, preparation environmental protection delayed cross-linking gel profile control agent is respectively charged in 8 wide-necked bottles; It is the thermostat container of differing temps (45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃) that wide-necked bottle is placed respectively Temperature Setting, and (temperature is 65 ℃, shearing rate 7.34s regularly to use Brookfield DV-III rotational viscosimeter
-1) measure the gelling strength of environmental protection delayed cross-linking gel profile control agent.Experimental result as shown in Figure 3, along with the rising of temperature, the gelling strength of environmental protection delayed cross-linking gel profile control agent weakens, but under 80 ℃, gelling strength still has 25600mPa.s, illustrates that this amendment has preferably heat resistance.
Embodiment 4: the salt resistant character of environmental protection delayed cross-linking gel profile control agent
Form the different salinity experimental waters of preparation according to the ion in the table 2, method according to preparation environmental protection delayed cross-linking gel profile control agent among the embodiment 1, experimental water preparation environmental protection delayed cross-linking gel profile control agent with preparation, be placed on respectively Temperature Setting and be in 65 ℃ the thermostat container, regularly with Brookfield DV-III rotational viscosimeter (65 ℃ of temperature, shearing rate 7.34s
-1) measure the gelling strength of environmental protection delayed cross-linking gel profile control agent.Experimental result as shown in Figure 4, the salinity of preparation water has by force certain impact to the one-tenth glue of amendment.The gelling strength of amendment that with salinity is the experimental water preparation of 5034.3mg/L is 31400mPa.s, the gelling strength that the salinity of experimental water is increased to amendment after 10 times is 18000mPa.s, illustrates that environmental protection delayed cross-linking gel profile control agent has certain salt resistant character.
The ion content of table 2 experimental water
Embodiment 5: the flow performance of environmental protection delayed cross-linking gel profile control agent
According to the preparation of the method among the embodiment 1 environmental protection delayed cross-linking gel profile control agent, in 65 ℃ of thermostat containers, to long 25cm, inject the amendment of preparation with 1.0ml/h speed in the one dimension sand-packed model of diameter 2.5cm, injection rate is 1.0 times of volume of voids; Until amendment becomes glue in the one dimension sand-packed model after, in the one dimension sand-packed model, inject preparation water with 1.0ml/h speed, the pressure change in the record experimentation.The flow performance curve of environmental protection delayed cross-linking gel profile control agent as shown in Figure 5.The porosity of one dimension sand-packed model is 28.23% before the profile control, and rate of permeation is 1.0958 μ m
2, the rate of permeation of one dimension sand-packed model is 4.8041 * 10-3 μ m after the injection profile agent
2, the sealing ratiod of amendment is 99.56%; The shutoff that amendment forms breaks through when pressure 1.3836MPa, and breakthrough pressure is higher; In addition, in follow-up water drive process, injection pressure illustrates that along with the increase of injection rate can remain on higher level this amendment has certain flushing resistance.
Claims (3)
1. environmental protection delayed cross-linking gel profile control agent is characterized in that the feed composition weight ratio is:
A, host hydrophobic associated polymer: 0.1%～0.4%;
B, linking agent Tiorco 677: 0.01%～0.02%;
C, antioxidant S-WAT: 0.015%～0.025%;
D, retardant sodium malate: 0.005%～0.020%;
E, all the other are water.
2. environmental protection delayed cross-linking gel profile control agent according to claim 1 is characterized in that, the molecular weight of hydrophobic association polymers is 8 * 10
6
3. environmental protection delayed cross-linking gel profile control agent according to claim 1 is characterized in that the preparation method is: the hydrophobic associated polymer mother liquor of preparation 0.5%, place behind the 24h stand-by; Prepare respectively 1.0% aluminum citrate solution, sodium sulfite solution and sodium malate solution; In wide-necked bottle, add successively a certain amount of hydrophobic associated polymer mother liquor, aluminum citrate solution, sodium sulfite solution, sodium malate solution and water; Wide-necked bottle is placed on stirs 15min on the magnetic stirring apparatus, prepare environmental protection delayed cross-linking gel profile control agent.
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Cited By (5)
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| CN104087280A (en) * | 2014-07-10 | 2014-10-08 | 中国石油大学(华东) | Blocking system and blocking method for channeling inhibition in carbon dioxide non-miscible flooding of low permeability reservoir |
| CN106433587A (en) * | 2016-09-18 | 2017-02-22 | 中国石油大学(华东) | Combined plugging agent |
| CN106479463A (en) * | 2016-09-19 | 2017-03-08 | 中国石油大学(华东) | Retarded crosslinking high intensity frozen glue profile-controlling and plugging agent |
| CN107502326A (en) * | 2017-09-04 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of secondary cross-linking carries liquid |
| CN114479801A (en) * | 2020-10-23 | 2022-05-13 | 中国石油天然气股份有限公司 | Full-liquid-phase high-temperature profile control agent and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087280A (en) * | 2014-07-10 | 2014-10-08 | 中国石油大学(华东) | Blocking system and blocking method for channeling inhibition in carbon dioxide non-miscible flooding of low permeability reservoir |
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| CN106433587A (en) * | 2016-09-18 | 2017-02-22 | 中国石油大学(华东) | Combined plugging agent |
| CN106479463A (en) * | 2016-09-19 | 2017-03-08 | 中国石油大学(华东) | Retarded crosslinking high intensity frozen glue profile-controlling and plugging agent |
| CN107502326A (en) * | 2017-09-04 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of secondary cross-linking carries liquid |
| CN114479801A (en) * | 2020-10-23 | 2022-05-13 | 中国石油天然气股份有限公司 | Full-liquid-phase high-temperature profile control agent and preparation method and application thereof |
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Application publication date: 20130313 |