CN1003048B - Zirconium gel water sealing agent - Google Patents
Zirconium gel water sealing agent Download PDFInfo
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- CN1003048B CN1003048B CN86108877A CN86108877A CN1003048B CN 1003048 B CN1003048 B CN 1003048B CN 86108877 A CN86108877 A CN 86108877A CN 86108877 A CN86108877 A CN 86108877A CN 1003048 B CN1003048 B CN 1003048B
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- China
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- zirconium
- water
- pam
- agent
- blocking agent
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Abstract
The present invention is composed of polyacrylamide (PAM) or methylene polyacrylamide (MPAM) used as gel forming agents and inorganic zirconium compounds used as cross-linking agents, wherein the inorganic zirconium compounds comprise zirconium oxychloride, zirconium tetrachloride, zirconium sulphate, zirconium nitrate, etc. Injection technology adopts a two-fluid method and has the advantages of convenient technology and safe construction, and blockage can be carried out as well as removed. The blocking agent not only can be used in an oil well for selective water blocking, but also can be used in a water injection well for the regulation of water absorbing profiles. The blocking agent has the advantages of favorable heat stability, high water blocking rate, strong absorbing property, water flushing resistance, long effective period, no toxicity and stimulation and low cost.
Description
The present invention relates to plugging agent.
As everyone knows, the essence of Water in Water Shutoff in Oil Field is to change the flow state of water in the stratum, to guarantee the stratum stable yields, reaches few water outlet, fecund oil, the purpose of raising oil field ultimate recovery factor.
The plugging agent that uses on the oil field has " selective water shutoff agent " and " non-selective plugging agent " at present, and its processing method has single-fluid process and two-fluid process.Polyacrylamide (PAM) is recalled in 1967 as a kind of outstanding plugging agent and is applied to oil field (U.S.P.3,308,885), has reached the purpose of selective water shut-off.But, easily washed away very soon, so the water blockoff validity period is very short by water because its adsorption film is not firm.In order to overcome this shortcoming, adopted the polyacrylamide plugging agent (O.G.J., VOI.73, NO.47,59-60,1975) of crosslinked (making linking agent) afterwards by chromium or aldehydes, effect is better.But along with the increase of degree of crosslinking, its selectivity variation, its one-tenth adhesive tape part is restricted big simultaneously, poor heat stability, toxic and pungency.
In recent years, on technology, take alternately to be injected into the method for jelly and linking agent again, gelatinizing agent polyacrylamide (PAM), linking agent Tiorco 677 (U.S.P.3,762,476).Its advantage is to change the number of times that alternately injects according to the size of zone permeability.But linking agent Tiorco 677 cost height, the source of goods is few, and crosslinked ability is relatively poor, and is little to the adsorptive power on stratum, still can not reach long validity period.
The purpose of this invention is to provide a kind of intensity height, Heat stability is good, adsorptive power is strong, water-fast washing away, validity period is long, and nontoxic nonirritant can be blocked up and can be separated, plugging agent with low cost.〉
The gelatinizing agent of plugging agent of the present invention is polyacrylamide (PAM) or type methylene polyacrylamide (MPAM), and linking agent is an inorganic zirconium compound, and it comprises: zirconium oxychloride (ZrOCL
28H
2O), zirconium tetrachloride (ZrCL
4), zirconium sulfate (Zr(SO
4)
24H
2O) and zirconium nitrate (Zr(NO
3)
45H
2O).
The working concentration of gelatinizing agent PAM or MPAM is that 0.3～2%(is heavy).The working concentration of cross-linking of inorganic zirconium compound is that 0.01～4%(is heavy).
Plugging agent of the present invention is in 100: 40～100(body with gelatinizing agent and linking agent) ratio, alternately inject the stratum with arbitrary sequencing.After two kinds of materials that enter the stratum met, the polynuclear hydroxy bridge complex ion of the zirconium that inorganic zirconium compound produces in water was crosslinked with gelatinizing agent PAM or MPAM.
Polynuclear hydroxy bridge complex ion
Since the valence mumber height (2n+6) of the polynuclear hydroxy bridge complex ion of zirconium, so it has stronger crosslinked ability than the aluminium of (n+4) valency or the polynuclear hydroxy bridge complex ion of chromium to PAM, therefore, the Heat stability is good of blocking agent, intensity height.Because of the stratum sandstone surface is electronegative, according to Schulze-Hardy valence mumber rule, (2n+6) polynuclear hydroxy bridge complex ion of the zirconium of nominal price is very strong to the adsorptive power of stratum sandstone surface again, so water-proof the washing away of energy, the water blockoff validity period is longer.
Plugging agent technology of the present invention is simple, and easy construction is safe and reliable, not only can be used for oilwell water shutoff, also can be used for water injection well and adjusts intake profile.Because this blocking agent is whole one-tenth glue (comprising water) when becoming glue, and in the process that degree of crosslinking increases gradually, blocking agent still can move forward, and produces further crosslinked.Thereby can make full use of medicament.The blocking agent usable acid of the present invention or the alkaline hydrolysis that enter the stratum remove.
Embodiment
Example 1
PAM or MPAM are under different concentration, to the influence such as the following table (table 1) of formed frozen glue.
Table 1 shows, 0.3～2.0% PAM or MPAM mix by a certain percentage with 0.01～4% zirconium compounds, stir with glass stick, all can become glue.
2. blocking agents of example see Table 2 to the stopping state of drill core permeability rate.
Table 2 blocking agent is to the stopping state of drill core permeability rate
Processing sequence K
1μ m
2K
2μ m
2Water plugging rate %
ZrOCL
2→PAM→ 0.637 0.007 98.9
ZrOCL
2→PAM
PAM→ZrOCL
2→
PAM→ZrOCL
2→ 0.694 0.002 99.7
PAM→ZrOCL
2
Table 2 shows, the permeability variation situation before and after core is handled with blocking agent of the present invention.K
1Be stifled preceding drill core permeability rate, K
2Be stifled back drill core permeability rate.Core is the glued sandstone of aluminum phosphate, length 35mm, diameter 25mm.Earlier core is vacuumized, saturation water is surveyed its rate of permeation K
1, alternately be injected into jelly and linking agent again, descended permanent 4 hours at 70 ℃ then, survey the rate of permeation K of the core after handling again
2Calculate water plugging rate with following formula at last
Water plugging rate=(K
1-K
2)/K
1100%
The concentration that table 2 injects is: PAM1.0%, ZrOCL
2Be 0.06%, each section consumption is 4ml.Down together.
Example 3
Water or the saturated core of oil have different breakthrough pressures after blocking agent of the present invention is handled.Be that the core entrance end slowly boosts, the pressure when exit end outflow first is dripped or be oily.Data list 3.
The breakthrough pressure of table 3 blocking agent in core
Processing sequence breakthrough pressure KPa
The saturation water saturated oil
ZrOCL
2→PAM→ZrOCL
2117.7 58.8
ZrOCL
2→PAM→ 343.2 304.0
ZrOCL
2→PAM
PAM→ZrOCL
2→PAM 196.1 49.0
PAM→ZrOCL
2→ 441.3 343.2
PAM→ZrOCL
2
Table 3 shows that the breakthrough pressure of saturated oil core is less than the breakthrough pressure of saturation water core.
Example 4 cores are handled with blocking agent of the present invention, and the permeability variation situation after water washes away sees Table 4
Table 4 washes away the drill core permeability rate influence of stifled back
Wash away volume, PV rate of permeation, 10
-3μ m
2
0 0.5
375 0.9
865 1.3
1250 9.8
1413 13.0
Rate of permeation is 9179 * 10 before stifled
-3μ m
2
Processing sequence is: PAM → ZrOCL
2→ PAM → ZrOCL
2→ PAM → ZrOCL
2
After 1413 times of volume of voids (PV) water washes away, its drill core permeability rate, still reach far away stifled before the permeability value of core, illustrating that this blocking agent is quite anti-washes away.
Plugging agent of the present invention both can be used for oilwell water shutoff, and had good selectivity, can be used for water injection well again and adjusted intake profile.Injection technology can adopt two-fluid process, and the precedence that two liquid inject can be selected arbitrarily, and the intermediary spacer pad does not need strict calculating, and technology is easy, and it is fool proof to construct, and the available general chemical process of mistake blocking layer section is removed.This blocking agent Heat stability is good, the water plugging rate height, adsorptivity is strong, and anti-local water washes away, and the water blockoff validity period is long, and blocking agent nontoxicity and pungency are with low cost.
Example 5
Gelatigenous blocking agent is put in the ampoule, under 70 ℃ of constant temperature, after three months, observes.Phenomenon sees Table 5.
The thermostability of table 5 blocking agent
Prescription frozen glue outward appearance, 70 ℃
Constant temperature three months
1.0%PAM+0.06%ZrOCL
2Frozen glue color, state are constant, have only minor amount of water to separate out
The same, but system saliferous 900PPm is the same
The same, system is saliferous not, and frozen glue color, state are not
But contain 7% reservoir sand change, anhydrous separating out
Table 5 shows that Zirconium gel has good thermostability.
Example 6
Get the frozen glue that 21.8 grams are generated by 40ml 1%PAM and 0.5ml 5% zirconium compounds, add the hydrochloric acid of 10ml 19%, under 70 ℃, the frozen glue water that has six/five body constituents to amass in one day.If add the sodium hydroxide of 10ml 20%, wholeization water in one day.Illustrate that Zirconium gel usable acid or alkaline hydrolysis remove.
Example 7
The cost of this blocking agent is low, and the cost of several main blocking agents of present on-the-spot usefulness is all at 74.5 yuan/m
3More than, this blocking agent is (with ZrOCL
28H
2O is an example) cost be 54.5 yuan/m
3Detailed data sees Table 6, table 7, table 8, table 9.
Table 6 F-HPAM blocking agent cost
Medicament title concentration consumption unit price computed monetary value of payments made in securities or in kind cost
% kg/m
3Unit/ton the common people/m
3
PAM 0.9 9 10000 90.0
HCHO 0.5 5 550 7.4 98.1
（37）%
HCL 0.7 7 100 0.7
（31）%
Table 7 PAM-Cr
+ 3The blocking agent cost
Medicament title concentration consumption unit price computed monetary value of payments made in securities or in kind cost
% kg/m
3Unit/ton the common people/m
3
PAM 0.7 7 10000 70.0
Na
2Cr
2O
70.09 0.9 1280 1.2 74.5
Na
2S
2O
30.14 1.4 550 0.5
Table 8 water glass-calcium chloride (two-fluid process) blocking agent cost
Medicament title concentration consumption unit price computed monetary value of payments made in securities or in kind cost
% kg/m
3Unit/ton the common people/m
3
250
Na
2SiO
310 100 （40）% 62.5 127.5
PAM 0.15 1.5 10000 15.0
CaCL
210 100 500 50.0
Claims (3)
1, a kind of by gelatinizing agent polyacrylamide or type methylene polyacrylamide (concentration of aqueous solution 0.3～2.0%(is heavy)) and the plugging agent formed of linking agent, it is characterized in that said linking agent is an inorganic zirconium compound.
2, plugging agent according to claim 1 is characterized in that said inorganic zirconium compound comprises zirconium oxychloride (ZrOCL
28H
2O), zirconium tetrachloride (ZrCL
4), zirconium sulfate (Zr(SO
4)
2.4H
2O) and zirconium nitrate (Zr(NO
3)
4.5H
2O).
3,, it is characterized in that the concentration that the said inorganic zirconium compound aqueous solution uses is heavy at 0.01～4%(according to claim 1,2 described plugging agents) scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86108877A CN1003048B (en) | 1986-12-31 | 1986-12-31 | Zirconium gel water sealing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86108877A CN1003048B (en) | 1986-12-31 | 1986-12-31 | Zirconium gel water sealing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108877A CN86108877A (en) | 1988-02-24 |
| CN1003048B true CN1003048B (en) | 1989-01-11 |
Family
ID=4804086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86108877A Expired CN1003048B (en) | 1986-12-31 | 1986-12-31 | Zirconium gel water sealing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003048B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055329C (en) * | 1997-10-21 | 2000-08-09 | 辽河石油勘探局钻采工艺研究院 | Single liquid method combined with two liquid method for water sealing in borehole |
| CN101220264B (en) * | 2007-12-18 | 2011-02-02 | 中国石油集团川庆钻探工程有限公司 | Method of producing acidic crosslinking agent for CO2 foam compression fracture |
| CN103205078A (en) * | 2013-04-15 | 2013-07-17 | 上海应用技术学院 | Ti-based polyacrylamide cross linking agent as well as preparation method and application thereof |
| CN105968258A (en) * | 2016-05-27 | 2016-09-28 | 济南科慧页岩化工技术有限公司 | Clean and environmentally friendly composite polymer for fracturing fluid and preparing method thereof |
| CN107814874B (en) * | 2017-11-01 | 2019-09-17 | 南阳理工学院 | A kind of nanoscale temperature-salty resisting cross-linked polymer microballoon and preparation method thereof |
-
1986
- 1986-12-31 CN CN86108877A patent/CN1003048B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86108877A (en) | 1988-02-24 |
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