CN100334139C - Intramolecular Al cross-linked polymer gel and its prepn - Google Patents
Intramolecular Al cross-linked polymer gel and its prepn Download PDFInfo
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- CN100334139C CN100334139C CNB2006100021338A CN200610002133A CN100334139C CN 100334139 C CN100334139 C CN 100334139C CN B2006100021338 A CNB2006100021338 A CN B2006100021338A CN 200610002133 A CN200610002133 A CN 200610002133A CN 100334139 C CN100334139 C CN 100334139C
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Abstract
The present invention relates to an intramolecular Al<3+> cross-linked polymer gel and a preparation method thereof. A gel cross-linked reaction is mainly generated among branched chains in the same polymer molecule, polymer gel with locality network molecule conformation exists, and the viscosity before and after gelling is basically constant. The gel can flow in a porous medium, flow resistance is obviously larger than that of polymer solutions with the same viscosity, and a residual resistance coefficient is larger than a resistance coefficient. The present invention is characterized in that the gel comprises the following components with mass percent: 0.04 to 0.08% of partial hydrolysis polyacrylamide, 0.01 to 0.04% of aluminum citrate, 0.05 to 1.0% of NaCl or KCl mineralization degree regulator and the balance of extraction sewage in an oil field. The gel prepared by the method is capable of effectively adjusting water injection profiles of water injection exploitation oil field wells and has good profile control characteristics.
Description
Technical field:
The present invention relates to a kind of auxiliary agent that the adjustment of water injection well in oil fields fluid entry profile or the displacement of reservoir oil are used, especially a kind of intramolecularly Al
3+Cross-linked polymer gel and method for making thereof.
Background technology:
Along with the continuous rising of domestic waterflooding oil field comprehensive water cut, how to reduce the main difficult technical that the swept volume that injects water poor efficiency and invalid circulation in most permeable zone or macropore, enlarges the centering low permeability layer has become oilfield development process.At present, the plugging agent (abbreviation amendment) of adjustment water injection well fluid entry profile commonly used mainly comprises Al on the oil field
3+, Cr
3+With polymer gel class and solid particulate class such as clay, oil well produced mud, flyash and the zeolite etc. of compound ion as linking agent.
Under indoor conditions, difference according to the aqueous solvent salinity, the crosslinking reaction of polymer molecule can be divided into two types of each interchain of same intramolecularly (intramolecularly) and each side chain interchains (intermolecular) of differing molecular, the former has " locality " network molecule configuration, compare with polymer phase, the gel molecular cyclotron radius is that viscosity changes not quite, but the flexibility of molecular chain is the deformability variation, and then resistance to flow increases when causing it to migrate in the duct, and this will help improving profile control effect.The latter has " regionality " network molecule configuration, the gel molecular cyclotron radius is that viscosity obviously increases, and much larger than the rock throat radius, it can not enter the rock duct under the normal displacement pressure, even if enter the duct under external force, its molecular structure also will be destroyed, and lose original profile control function.
Compare with indoor conditions, mining site preparation with becomes the glue process to be subjected to oil reservoir " complicated chemical environment ", the pore space environment of poor continuity " small and " and aspect factors such as " mobile and shearing actions " to restrict, cause oil reservoir interpolymer molecule can't realize " intermolecular " crosslinking reaction on a large scale, " intramolecularly " crosslinking reaction also becomes difficult unusually, and this is the relatively poor basic reason of cross-linked polymer mining site effect.
In oil reservoir, can't form and have " regionality " network molecule configuration polymer gel, it is also very difficult that formation has " locality " network molecule configuration polymer gel, and the polymer gel with " regionality " network molecule configuration that make on ground can not enter reservoir of porous medium.Therefore, adopting ground to make " intramolecularly " cross-linked polymer gel is the important channel of improving the transfer drive effect.
Summary of the invention:
The objective of the invention is to solve the deficiencies in the prior art, a kind of intramolecularly Al is provided
3+Cross-linked polymer gel and method for making thereof, this gel crosslinking reaction mainly occurs in inner each interchain of same polymer molecule and has " locality " network molecule configuration polymer gel, viscosity remains unchanged substantially before and after becoming glue, gel can flow in porous medium, resistance to flow is obviously greater than the polymers soln of identical viscosity, and residual resistance factor is greater than resistance coefficient.
The technical solution adopted in the present invention is: this intramolecularly Al
3+Cross-linked polymer gel, it is characterized in that: comprise following each component: following each component is proportioning by mass percentage: partially hydrolyzed polyacrylamide 0.04%～0.08%, Tiorco 677 0.01%～0.04%, salinity conditioning agent NaCl or KCl 0.05～1.0%, surplus is an oilfield produced waste water.。
The above-mentioned thiocarbamide 0.002%～0.016% that also comprises; The polymkeric substance relative molecular mass is 500 * 10
4～3800 * 10
4, degree of hydrolysis is between 15%～28%.
The preparation method of above-mentioned gel is: after above-mentioned each component is mixed on the ground, deposit 3～5 days precast gels, inject the stratum then.
The invention has the beneficial effects as follows: take technique scheme, be mixed with gel on ground in advance, crosslinking reaction mainly occurs in inner each interchain of same polymer molecule, formation has " locality " network molecule configuration polymer gel, placed 3～5 days, and became before and after the glue viscosity this polymer gel that remains unchanged substantially to have characteristics such as viscosity is low, resistance to flow is big; Inject the oil reservoir porous medium then, gel can flow in porous medium, and resistance to flow is obviously greater than the polymers soln of identical viscosity, and residual resistance factor can effectively be adjusted the waterflooding oil field profile-log of water injection greater than resistance coefficient.Show good profile control characteristic.
Below be the contrast experiment that polymer gel and polymers soln are done: polymer concentration C in the polymer gel
P=500mg/l, Al
3+Concentration C=15mg/l, thiourea concentration C
Thiocarbamide=80mg/l, salinity conditioning agent NaCl or KCl 0.05%, surplus is an oilfield produced waste water.Polymers soln interpolymer concentration is 500mg/l.Following experimental data is to record with conventional viscosity measurement, ion composition measuring method and experiment condition:
Experiment is taken from Daqing oil field second oil recovery factory with sewage and clear water, and its mineral composition sees Table 1.
Table 1 sewage and clear water ion are formed
| Ion is formed | Ionic concn (mg/l) | |
| Clear water | Sewage | |
| CO 3 | 15.3 | 324.1 |
| HCO 3 | 389.0 | 1770.8 |
| Cl | 106.4 | 567.4 |
| SO 1 | 57.6 | 38.4 |
| Ca | 12.0 | 22.0 |
| Mg | 4.9 | 8.5 |
| Na+K | 231.9 | 1260.9 |
| Total mineralization | 817.1 | 3992.1 |
Table 2 polymers soln and gel viscosity and timing relationship
| Solution type | Time (d) | ||||||||
| Viscosity (mPas) | |||||||||
| Initial stage | 2d | 5d | 8d | 14d | 20d | 30d | 45d | 60d | |
| The sewage gel | 6.6 | 6.2 | 5.5 | 4.8 | 4.6 | 4.8 | 4.8 | 6.1 | 6.2 |
| The clear water gel | 13.6 | 13.3 | 13.2 | 48.0 | 3×10 4 | 6×10 4 | 9×10 4 | 9×10 4 | 6×10 4 |
| The sewage polymers soln | 7.2 | 6.4 | 5.4 | 4.2 | 3.7 | 3.5 | 3.2 | 3.8 | 3.7 |
| The clear water polymers soln | 15.2 | 14.4 | 13.8 | 11.5 | 8.2 | 7.0 | 6.5 | 6.0 | 6.1 |
For polymers soln, in the prior art, with the clear water preparation, and do not use the salinity conditioning agent, for example documents 1CN1270967A.Data no matter be that the polymers soln viscosity all increases in time and reduces with clear water or sewage preparation, but the reservation viscosity of clear water polymers soln are wanted the big of ratio sewage polymers soln as can be seen from table 1 and table 2.Sewage polymer gel viscosity changes not quite in time, and the viscosity of clear water prepared polymer gel increases in time and increases, and high viscosity can reach 10
4MPas.From the viscosity numerical value change, can determine Al in the clear water
3+Formed " intermolecular " cross-linked polymer gel with the polymer molecule effect.And in the documents 1 openly gel be that " intramolecularly " is crosslinked and narrate its nature and characteristic, the rock core blocking experiment is only disclosed.But, just can't judge Al only according to viscosity numerical value for the polymer gel of sewage preparation
3+Crosslinking reaction situation with polymer molecule.
It is resistance coefficient and residual resistance factor test result that table 3 provides the flow characteristics of sewage gel and polymers soln.
Table 3 resistance coefficient F
RWith residual resistance factor F
RRTest result
| Solution | The 1st day | The 2nd day | The 5th day | The 10th day | ||||
| F R | F RR | F R | F RR | F R | F RR | F R | F RR | |
| The sewage gel | 4.9 | 2.3 | 5.2 | 5.8 | 7.3 | 28.4 | 192.4 | 271.2 |
| The sewage polymers soln | 5.5 | 1.6 | 4.9 | 1.6 | 5.2 | 1.6 | 4.9 | 1.5 |
Rock core perm-plug method 800 * 10
-3μ m
2
From table 2 and table 3 as can be seen, though the sewage polymer gel is compared with polymers soln, the viscosity difference is little, and the former resistance coefficient and residual resistance factor value be obviously greater than the latter, and pressure reduction also increased continuing when follow-up water drive was described.In addition, sewage polymer gel resistance coefficient and residual resistance factor numerical values recited relation is opposite with the sewage polymers soln just, and the difference that this has reflected polymkeric substance and gel molecular structure illustrates that the sewage polymer gel is " intramolecularly " corsslinking molecular configuration.Compare with the clear water polymer gel, sewage polymer gel molecule cyclotron radius is that viscosity changes not quite, but the flexibility of molecular chain is the deformability variation, and then resistance to flow increases when causing it to migrate in the duct, and this character is very beneficial for improving profile control effect.Those skilled in the art thought that sewage prepared polymer can not become glue in the past, and its reason is that viscosity does not have considerable change.The present invention has overcome forefathers' technology prejudice in fact, recognizes that " intramolecularly " cross-linked polymer viscosity can obviously not increase, and can not continue to use traditional viscosity index and estimate polymkeric substance and become the glue effect.From experiment of the present invention as can be seen, list can not be distinguished " intramolecularly " cross-linked polymer gel and general polymer solution from viscosity index, so the present invention proposes the resistance coefficient F of factory
RWith residual resistance factor F
RRAs evaluation index.
Resistance coefficient F
RWith residual resistance factor F
RRBe the mining site evaluation polymkeric substance commonly used and the index of cross-linked polymer performance characteristic, it is defined as follows:
δ P wherein
1Be rock core water drive pressure reduction, δ P
2For polymkeric substance or gel drive pressure reduction, δ P
3Be follow-up water drive pressure reduction.
Embodiment:
Be further described this intramolecularly Al below in conjunction with specific embodiment
3+Cross-linked polymer gel comprises following each component: following each component is proportioning by mass percentage: partially hydrolyzed polyacrylamide 0.04%～0.08%, Tiorco 677 0.01%～0.04%, salinity conditioning agent NaCl or KCl 0.05～1.0%, surplus is an oilfield produced waste water.For making profile control reach better effect, also add thiocarbamide 0.002%～0.016% in the present invention.Partially hydrolyzed polyacrylamide is 500 * 10
4～3800 * 10
4, degree of hydrolysis between 15%～28%, solid content 91.7%.Partially hydrolyzed polyacrylamide is that HPAM is produced by the Daqing oil field auxiliary reagent factory.Tiorco 677 (AlC
6H
5O
73H
2O) use as linking agent, the aluminium effective content is 1%.
Preparation method of the present invention is: after above-mentioned each component is mixed on the ground, deposit 3～5 days precast gels, inject the stratum then.Overcome the technology prejudice of in the past preparing at mining site, mining site preparation with becomes the glue process to be subjected to oil reservoir " complicated chemical environment ", the pore space environment of poor continuity " small and " and aspect factors such as " mobile and shearing actions " to restrict, cause oil reservoir interpolymer molecule can't realize " intermolecular " crosslinking reaction on a large scale, " intramolecularly " crosslinking reaction also becomes difficult unusually, and this is the relatively poor basic reason of cross-linked polymer mining site effect.
Embodiment 1, partially hydrolyzed polyacrylamide 0.4 gram, Tiorco 677 0.1 gram, sodium-chlor 1.0 grams and sewage 998.5 grams are mixed on the ground after, place and inject rock core after 3 days.
Embodiment 2, partially hydrolyzed polyacrylamide 0.5 gram, Tiorco 677 0.15 gram, thiocarbamide 0.08, sodium-chlor 1.0 grams and sewage 998.27 grams are mixed on the ground after, place and inject rock core after 3 days.
Embodiment 3, partially hydrolyzed polyacrylamide 0.8 gram, Tiorco 677 0.4 gram, thiocarbamide 0.16 gram, sodium-chlor 1.0 grams and sewage 997.64 grams are mixed on the ground after, place and inject rock core after 3 days.
Embodiment 4, partially hydrolyzed polyacrylamide 0.5 gram, Tiorco 677 0.15 gram, thiocarbamide 0.02 gram, Repone K 1.0 grams and sewage 998.33 grams are mixed on the ground after, place and inject rock core after 3 days.
Embodiment 5, partially hydrolyzed polyacrylamide 0.8 gram, Tiorco 677 0.4 gram, Repone K 1.0 grams and sewage 997.8 grams are mixed on the ground after, place and inject rock core after 3 days.
Embodiment 5, partially hydrolyzed polyacrylamide 0.8 gram, Tiorco 677 0.4 gram and sewage 998.8 grams are mixed on the ground after, place and inject rock core after 3 days.
Claims (3)
1, a kind of intramolecularly Al
3+Cross-linked polymer gel is characterized in that: comprise following each component: following each component is proportioning by mass percentage: partially hydrolyzed polyacrylamide 0.04%～0.08%, molecular mass are 500 * 10
4～3800 * 10
1, degree of hydrolysis between 15%～28%, Tiorco 677 0.01%～0.04%, salinity conditioning agent NaCl or KCl 0.05～1.0%, surplus is an oilfield produced waste water.
2, according to the described intramolecularly Al of right l
3+Cross-linked polymer gel is characterized in that: also comprise thiocarbamide 0.002%～0.016%.
3, according to right 1 or 2 described intramolecularly Al
3+The preparation method of cross-linked polymer gel is characterized in that: after above-mentioned each component is mixed on the ground, deposit 3～5 days precast gels, inject the stratum then.
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| CN100334139C true CN100334139C (en) | 2007-08-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533233A (en) * | 2012-01-04 | 2012-07-04 | 中国石油天然气股份有限公司 | High-temperature-resistant high-salinity water shutoff profile control agent and preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604609B (en) * | 2012-02-07 | 2014-11-19 | 中国石油天然气股份有限公司 | Different-part cross-linking water shutoff profile control gel and preparation method thereof |
| CN103408881B (en) * | 2013-08-14 | 2015-09-02 | 中国海洋石油总公司 | A kind of Organic/inorganic composite colloidal dispersion gel and preparation method thereof |
| CN103694974A (en) * | 2013-12-04 | 2014-04-02 | 天津大港油田滨港集团博弘石油化工有限公司 | Chromium-free crosslinking system |
| CN106085393A (en) * | 2016-06-06 | 2016-11-09 | 关俊华 | A kind of preparation method of positive colloid water shutoff agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526231A (en) * | 1983-07-25 | 1985-07-02 | The United States Of America As Represented By The United States Department Of Energy | Process for tertiary oil recovery using tall oil pitch |
| CN1197101A (en) * | 1997-04-22 | 1998-10-28 | 高英敏 | Application of cross-linking agent in polymer displacement of reservoir oil tech. |
| CN1278545A (en) * | 2000-03-24 | 2001-01-03 | 大庆油田有限责任公司采油工艺研究所 | Flowable depth profile control agent |
| CN1537883A (en) * | 2003-10-21 | 2004-10-20 | 石油大学(北京) | Preparation method of cross-linking polymer solution suitable for high temperature condition |
-
2006
- 2006-01-19 CN CNB2006100021338A patent/CN100334139C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526231A (en) * | 1983-07-25 | 1985-07-02 | The United States Of America As Represented By The United States Department Of Energy | Process for tertiary oil recovery using tall oil pitch |
| CN1197101A (en) * | 1997-04-22 | 1998-10-28 | 高英敏 | Application of cross-linking agent in polymer displacement of reservoir oil tech. |
| CN1278545A (en) * | 2000-03-24 | 2001-01-03 | 大庆油田有限责任公司采油工艺研究所 | Flowable depth profile control agent |
| CN1537883A (en) * | 2003-10-21 | 2004-10-20 | 石油大学(北京) | Preparation method of cross-linking polymer solution suitable for high temperature condition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533233A (en) * | 2012-01-04 | 2012-07-04 | 中国石油天然气股份有限公司 | High-temperature-resistant high-salinity water shutoff profile control agent and preparation method and application thereof |
| CN102533233B (en) * | 2012-01-04 | 2014-11-05 | 中国石油天然气股份有限公司 | High-temperature-resistant high-salinity water shutoff profile control agent and preparation method and application thereof |
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| CN1810918A (en) | 2006-08-02 |
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