CN104987857A - High-salinity-resistant self-tackifying hydrophobically associating polymer gel plugging agent and preparing method thereof - Google Patents
High-salinity-resistant self-tackifying hydrophobically associating polymer gel plugging agent and preparing method thereof Download PDFInfo
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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
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Abstract
The invention provides a high-salinity-resistant self-tackifying hydrophobically associating polymer gel plugging agent and a preparing method thereof. The plugging agent comprises, by weight, 0.25-0.45% of a base resin hydrophobically associating polymer, 0.40-0.80% of cross-linking agent polyethyleneimine, 0.10-0.30% of initiator persulfate, 0.20-0.50% of performance modifier low-molecule alcohol and the balance saline. The preparing method of the plugging agent comprises the steps that hydrophobically associating polymer mother liquor and polyethyleneimine mother liquor are prepared; an initiator and a performance modifier are dissolved into the saline; the hydrophobically associating polymer mother liquor of the needed amount and the polyethyleneimine mother liquor of the needed amount are added; the mixture is sealed, and stands to form gel to obtain the plugging agent. According to the gel plugging agent, under the high-salinity condition, the tackifying and gel forming effects are good, the plugging performance is high, the plugging agent is stable for a long term, suitable for profile control and water plugging operation under the high-salinity condition, flow preferential migration passages in high-salinity stratums can be effectively plugged, and the spread effect of injected water is improved.
Description
Technical field
The present invention relates to a kind of plugging agent of oil field use and preparation method thereof, particularly the resistance to high salt of one is from tack-producing hydrophobic association polymer Gel profile control agent and preparation method thereof, belongs to technical field of oilfield chemistry.
Background technology
Maturing field, after the waterflooding of decades, owing to injecting constantly washing away of water, can produce the current predominant pathway such as a large amount of macropores or microfracture in oil reservoir.Follow-up injection water can charge into oil well too early along the flowing of current predominant pathway, and this not only can cause and inject the reduction of water impact scope, water ratio in oil well also can be made to increase too fast, finally reduce oil recovery factor.Profile Control in Injection Well and oilwell water shutoff are one of effective ways improving floood conformance effect.The effect of profile control and water plugging not only depends on injection technology, also depends primarily on the performance of plugging agent.Along with the profile control and water plugging job task amount on oil field high salinity stratum in recent years increases year by year, whether successfully resistance to high salt plugging agent becomes operation one of key point.
Gel-like plugging agent is one of conventional plugging agent type in oil field, and the most widely used is for polymkeric substance and the gelling system that forms for linking agent with metal ion or phenolic aldehyde with partially hydrolyzed polyacrylamide (HPAM).But, because the salt resistant character of HPAM is poor, be that the result of use of gelling system in high salinity block of polymkeric substance is not good with HPAM.Recent domestic scholar does a lot of work for the research and development of the plugging agent of resistance to high salinity.CN10449618A discloses a kind of composite with materials such as acrylamide (AM) monomer and ester class, alcohols, that prepares under the effect of initiator can the gelling system of high temperature resistant, high salinity condition, but this gelling system complicated component, and not easily prepare under normal temperature condition.Particulate species plugging agent is also plugging agent type conventional at present.CN104479664A discloses the organic granular blocking agent that a kind of main component is organic phenol, formaldehyde, furfural etc.; CN104341548A discloses a kind of copolymerization microsphere; Although this kind of particle blocking agent salt resistant character is better, synthesis technique is complicated, and cost is higher, and application economic benefit is not as good as Gelling Plugging Agent.
Therefore, develop a kind of Gel profile control agent, make it have the performances such as resistance to high salt, become one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of resistance to high salt from tack-producing hydrophobic association polymer Gel profile control agent and preparation method thereof.This plugging agent thickening plastic under high salt condition is respond well, and sealing characteristics is higher, and stable performance.
For achieving the above object, the invention provides a kind of resistance to high salt from tack-producing hydrophobic association polymer Gel profile control agent, with the gross weight of this plugging agent for benchmark, its raw material composition comprises:
Host: hydrophobic associated polymer 0.25-0.45wt%,
Linking agent: polymine 0.40-0.80wt%,
Initiator: persulphate 0.10-0.30wt%,
Properties modifier: low mass molecule alcohol 0.20-0.50wt% and
Salt water surplus.
At above-mentioned resistance to high salt in tack-producing hydrophobic association polymer Gel profile control agent, preferably, described hydrophobic associated polymer comprises allyl group ammonium type hydrophobic associated polymer.This allyl group ammonium type hydrophobic associated polymer is the terpolymer of acrylamide, vinylformic acid and the pungent ammonium of allyl dimethyl base.More preferably, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1200-1500 ten thousand, and degree of hydrolysis is 23-27mol%, and hydrophobic association group content is 1.7-2.1mol%.
At above-mentioned resistance to high salt in tack-producing hydrophobic association polymer Gel profile control agent, preferably, the relative molecular mass of described polymine is 2-5 ten thousand.
At above-mentioned resistance to high salt in tack-producing hydrophobic association polymer Gel profile control agent, preferably, described low mass molecule alcohol comprises the combination of one or more in ethanol, propyl alcohol, glycerol and propyl carbinol etc.If it is two or more that described low mass molecule alcohol comprises in above-mentioned substance, then they can arbitrary proportion mixing.
In the present invention, low mass molecule alcohol mainly plays the effect of two aspects: (1) low mass molecule alcohol can regulate the hydrophobicity of hydrophobic grouping on hydrophobic associated polymer, and low mass molecule alcohol can be used to affect the hydrophobic association effect of hydrophobic associated polymer; (2) low mass molecule alcohol can strengthen hydrophobic associated polymer (especially carboxyl) diffusion double layer effect around, thickens hydration shell, thus strengthens polymkeric substance to the resistant function of salt ion, and then can strengthen the stability of gel.
At above-mentioned resistance to high salt in tack-producing hydrophobic association polymer Gel profile control agent, preferably, described persulphate comprises the combination of one or more in Sodium Persulfate, ammonium persulphate and Potassium Persulphate etc.If it is two or more that described persulphate comprises in above-mentioned substance, then they can arbitrary proportion mixing.
At above-mentioned resistance to high salt in tack-producing hydrophobic association polymer Gel profile control agent, preferably, described salt solution comprises sodium ion that concentration is 0-1000000mg/L (being more preferably 0-80000mg/L), concentration is one or both combination in calcium ion of 0-1000mg/L etc.The present invention selects hydrophobic associated polymer as polymkeric substance, and polymine, as linking agent, under initiator and properties modifier effect, crosslinking reaction occurs, and obtains a kind ofly having the hydrophobic associated polymer Gel profile control agent of resistance to high salt from thickening character.The hydrophobic associated polymer that the present invention adopts, due to the existence of hydrophobic grouping, it has special physico-chemical property, under high salt condition, between the hydrophobic grouping of hydrophobic associated polymer, hydrophobic association occurs, makes plugging agent thickening; Under initiator effect, hydrophobic associated polymer and polymine generation crosslinking reaction generate high strength spacial framework, reach the effect of underground self-crosslinking, and final generation has the gel of resistance to high salt from thickening character.
The present invention also provides above-mentioned resistance to high salt from the preparation method of tack-producing hydrophobic association polymer Gel profile control agent, and it comprises the following steps:
(1) hydrophobic associated polymer mother liquor and polymine mother liquor is prepared;
(2) according to described resistance to high the salt weight percentage of initiator and properties modifier and ionic concn of salt solution in tack-producing hydrophobic association polymer Gel profile control agent, initiator and properties modifier are dissolved in salt solution, obtain a mixed solution A;
(3) according to the weight percentage of described resistance to high salt hydrophobic associated polymer and polymine in tack-producing hydrophobic association polymer Gel profile control agent, the hydrophobic associated polymer mother liquor of aequum and the polymine mother liquor of aequum is added in the mixed solution A that step (2) obtains, stir, obtain a mixing solutions B;
(4) the mixing solutions B that step (3) obtains is placed in encloses container, leaves standstill, after its plastic, obtain described resistance to high salt from tack-producing hydrophobic association polymer Gel profile control agent.
In the present invention, prepare described resistance to high salt when tack-producing hydrophobic association polymer Gel profile control agent, must carry out in strict accordance with the step in aforesaid method, this preparation method can affect the performance of obtained plugging agent.
In above-mentioned preparation method, preferably, the mass concentration of the hydrophobic associated polymer mother liquor in step (1) is 1.0-3.0wt%, and the mass concentration of polymine mother liquor is 1.5-4.0wt%.Saline hydrophobic associated polymer mother liquor and polymine mother liquor can be adopted, as long as make the ionic concn in the Gel profile control agent finally had to meet the demands.
In above-mentioned preparation method, preferably, step (1) also comprises: by the hydrophobic associated polymer mother liquor for preparing and polymine mother liquor slaking 10-20h at 10-30 DEG C respectively.
In above-mentioned preparation method, preferably, the temperature left standstill in step (4) is 70-90 DEG C, and the time is 0-100h.The process left standstill can be carried out in an oven.
Resistance to high salt provided by the invention mainly has following beneficial effect from tack-producing hydrophobic association polymer Gel profile control agent:
(1) resistance to high salt of the present invention can from thickening plastic under the condition of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L from tack-producing hydrophobic association polymer Gel profile control agent, and after plastic, gel apparent viscosity is greater than 15000mPas;
(2) resistance to high salt of the present invention is from the stable performance under high salt condition of tack-producing hydrophobic association polymer Gel profile control agent, and in 80 days, obvious reduction does not occur viscosity;
(3) resistance to high salt of the present invention is 30-80h from the gelation time of tack-producing hydrophobic association polymer Gel profile control agent under 80 DEG C of conditions;
(4) resistance to high salt of the present invention is greater than 98% from the sealing ratiod of tack-producing hydrophobic association polymer Gel profile control agent to rock core, and sequent water flooding breakthrough pressure gradient is higher than 20MPa/m.
In sum, resistance to high salt provided by the invention is from tack-producing hydrophobic association polymer Gel profile control agent, under high salt condition, thickening plastic is respond well, sealing characteristics is higher, and there are permanent stability, be suitable for use as the plugging agent of profile control water-blocking operation under high salt condition, can the current predominant pathway such as macropore, crack in effectively shutoff high salinity stratum, improve and inject water spread effect.This amendment effectively can expand the scope of application of gel-type plugging agent in oil field, has good application prospect, and can obtain good economic benefit.
Accompanying drawing explanation
Fig. 1 is the apparent viscosity over time graph of a relation of the resistance to high salt in embodiment 1 from tack-producing hydrophobic association polymer Gel profile control agent;
Fig. 2 is the apparent viscosity over time graph of a relation of the resistance to high salt in embodiment 2 from tack-producing hydrophobic association polymer Gel profile control agent;
Fig. 3 is the apparent viscosity over time graph of a relation of the resistance to high salt in embodiment 3 from tack-producing hydrophobic association polymer Gel profile control agent;
Fig. 4 is the apparent viscosity over time graph of a relation of the resistance to high salt in embodiment 4 from tack-producing hydrophobic association polymer Gel profile control agent;
Fig. 5 is the apparent viscosity over time graph of a relation of the resistance to high salt in embodiment 5 from tack-producing hydrophobic association polymer Gel profile control agent.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
The reservoir core plugging performance test related in following examples, the rock core used is fill out sand tube rock core, and test procedure is:
(1) 40-60 order, 60-80 order, 100-120 order three kinds of quartz sands are used to be filled in the fill out sand tube that diameter D is 2.5cm, length L is 30cm respectively, the obtained fill out sand tube rock core with different rate of permeation;
(2) vacuumize that rear saturated Na ion concentration is 80000mg/L, calcium ion concn is the salt solution of 1000mg/L, the volume of voids V and the initial water that record each fill out sand tube rock core survey rate of permeation K
0;
(3) be injected in each rock core by Gel profile control agent solution freshly prepared in embodiment, injection rate is the rock pore volume of 0.6 times;
(4) sealed at basket two ends, be placed in 80 DEG C of thermostatic drying chambers and treat its plastic, time of repose is the gelation time of Gel profile control agent solution;
(5) rock core injects in the other direction the salt solution that Na ion concentration is 80000mg/L, calcium ion concn is 1000mg/L and carries out displacement test, records breakthrough pressure P
break throughwith follow-up steady injection pressure P
steadily;
(6) calculate breakthrough pressure gradient dP/dL (MPa/m) according to formula (1), after calculating shutoff according to Darcy formula, water surveys rate of permeation K
1, and then calculate reservoir core plugging rate F (%) according to formula (2).
DP/dL=P
break through/ L (1)
Embodiment 1
One, the preparation of Gel profile control agent 1
With the gross weight of Gel profile control agent 1 for benchmark, its raw material consists of: allyl group ammonium type hydrophobic associated polymer 0.25%, polymine 0.40%, Sodium Persulfate 0.10%, propyl carbinol 0.20%, and surplus is the salt solution of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L.Wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1,300 ten thousand, and degree of hydrolysis is 23-27%, and hydrophobic association group content is 1.8wt%; The relative molecular mass of described polymine is 20,000.
The preparation method of this Gel profile control agent 1 is:
(1) salt solution (ionic concn is considered ionic concn in last obtained Gel profile control agent and prepares) preparation hydrophobic associated polymer mother liquor mass concentration is first used to be 2.0wt%, polymine mother liquor mass concentration is 2.0wt%, respectively slaking 12h under normal temperature;
(2) calculate required for hydrophobic associated polymer mother liquor, polymine mother liquor and preparation mother liquor after the remaining salt solution number that accounts for Gel profile control agent cumulative volume be respectively 12.5 parts, 20 parts and 67.5 parts;
(3) with the gross weight of described Gel profile control agent for benchmark, the Sodium Persulfate of 0.10% and the propyl carbinol of 0.20% are dissolved in the salt solution of 67.5 parts by volume, stir;
(4) by the hydrophobic associated polymer mother liquor of 12.5 parts by volume and and the polymine mother liquor of 20 parts by volume join successively in the solution that step (3) obtains, stir, namely obtain freshly prepared Gel profile control agent 1 solution;
(5) solution that step (4) obtains is poured in vial seal;
(6) vial is positioned in the constant temperature oven of 80 DEG C, treats its standing plastic, namely obtain the resistance to high salt of the present embodiment from tack-producing hydrophobic association polymer Gel profile control agent 1.
Two, Gel profile control agent 1 from thickening property
Shown in Fig. 1 be different time of repose time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of this Gel profile control agent recorded under condition.After leaving standstill 20h, gel viscosity starts remarkable rising, shows that now starting gel component crosslinking reaction speed accelerates; After leaving standstill 80h, gel viscosity amplification reduces, and show that now gel component reaction is close to complete, gelation time is 80h, and gel apparent viscosity now reaches 15780mPas; Gel apparent viscosity when leaving standstill 100h is 16490mPas.
Three, the reservoir core plugging performance of Gel profile control agent 1
Shown in table 1 is the sealing characteristics parameter of Gel profile control agent 1 to three kinds of different rate of permeation fill out sand tube rock cores.
The reservoir core plugging performance perameter of table 1 Gel profile control agent 1
| Numbering | 1 | 2 | 3 |
| Core permeability, μm 2 | 5.23 | 1.25 | 0.54 |
| Breakthrough pressure gradient, MPa/m | 20.52 | 21.86 | 21.81 |
| Reservoir core plugging rate, % | 98.04 | 98.26 | 99.49 |
As seen from Table 1, the breakthrough pressure gradient of Gel profile control agent 1, higher than 20MPa/m, to the sealing ratiod of the fill out sand tube rock core of three kinds of rate of permeation ranks all more than 98%, has good reservoir core plugging performance.
Four, the stability of Gel profile control agent 1
Be respectively charged in 6 vials by freshly prepared Gel profile control agent 1 solution that the present embodiment is prepared and seal, the liquor capacity in each vial is 100mL; Vial is positioned in the constant temperature oven of 80 DEG C, takes out when specified time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of Gel profile control agent is tested under condition.Namely shown in table 2 is the viscosity data of Gel profile control agent 1 when leaving standstill different time.
The stability parameter of table 2 Gel profile control agent 1
| Leave standstill number of days, d | 20 | 40 | 60 | 80 | 100 | 150 |
| Apparent viscosity, mPas | 16380 | 16145 | 15765 | 15448 | 14020 | 11190 |
As seen from Table 2, in leaving standstill 80 days, the apparent viscosity of Gel profile control agent 1 is all higher than 15000mPas, and obvious reduction does not occur viscosity, shows that Gel profile control agent 1 has good stability.
Embodiment 2
One, the preparation of Gel profile control agent 2
With the gross weight of Gel profile control agent 2 for benchmark, its raw material consists of: allyl group ammonium type hydrophobic associated polymer 0.30%, polymine 0.50%, ammonium persulphate 0.20%, propyl carbinol 0.30%, and surplus is the salt solution of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L.Wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1,300 ten thousand, and degree of hydrolysis is 23-27%, and hydrophobic association group content is 1.8wt%; The relative molecular mass of described polymine is 20,000.
The preparation method of this Gel profile control agent 2 is:
(1) salt solution (ionic concn is considered ionic concn in last obtained Gel profile control agent and prepares) preparation hydrophobic associated polymer mother liquor mass concentration is first used to be 2.0wt%, polymine mother liquor mass concentration is 2.0wt%, respectively slaking 12h under normal temperature;
(2) calculate required for hydrophobic associated polymer mother liquor, polymine mother liquor and preparation mother liquor after the remaining salt solution number that accounts for Gel profile control agent cumulative volume be respectively 15 parts, 25 parts and 60 parts;
(3) with the gross weight of described Gel profile control agent for benchmark, the ammonium persulphate of 0.20% and the propyl carbinol of 0.30% are dissolved in the salt solution of 60 parts by volume, stir;
(4) by the hydrophobic associated polymer mother liquor of 15 parts by volume and and the polymine mother liquor of 25 parts by volume join successively in the solution that step (3) obtains, stir, namely obtain freshly prepared Gel profile control agent 2 solution;
(5) solution that step (4) obtains is poured in vial seal;
(6) vial is positioned in the constant temperature oven of 80 DEG C, treats its standing plastic, namely obtain the resistance to high salt of the present embodiment from tack-producing hydrophobic association polymer Gel profile control agent 2.
Two, Gel profile control agent 2 from thickening property
Shown in Fig. 2 be different time of repose time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of this Gel profile control agent recorded under condition.After leaving standstill 20h, gel viscosity starts remarkable rising, shows that now starting gel component crosslinking reaction speed accelerates; After leaving standstill 60h, gel viscosity amplification reduces, and show that now gel component reaction is close to complete, gelation time is 60h, and gel apparent viscosity now reaches 17870mPas; Gel apparent viscosity when leaving standstill 100h is 18305mPas.
Three, the reservoir core plugging performance of Gel profile control agent 2
Shown in table 3 is the sealing characteristics parameter of Gel profile control agent 2 to three kinds of different rate of permeation fill out sand tube rock cores.
The reservoir core plugging performance perameter of table 3 Gel profile control agent 2
| Numbering | 1 | 2 | 3 |
| Core permeability, μm 2 | 5.56 | 1.18 | 0.61 |
| Breakthrough pressure gradient, MPa/m | 21.52 | 23.18 | 25.89 |
| Reservoir core plugging rate, % | 98.89 | 99.75 | 99.91 |
As seen from Table 3, the breakthrough pressure gradient of Gel profile control agent 2, higher than 22MPa/m, to the sealing ratiod of the fill out sand tube rock core of three kinds of rate of permeation ranks all more than 98.8%, has good reservoir core plugging performance.
Four, the stability of Gel profile control agent 2
Be respectively charged in 6 vials by freshly prepared Gel profile control agent 1 solution that the present embodiment is prepared and seal, the liquor capacity in each vial is 100mL; Vial is positioned in the constant temperature oven of 80 DEG C, takes out when specified time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of Gel profile control agent is tested under condition.Namely shown in table 4 is the viscosity data of Gel profile control agent 2 when leaving standstill different time.
The stability parameter of table 4 Gel profile control agent 2
| Leave standstill number of days, d | 20 | 40 | 60 | 80 | 100 | 150 |
| Apparent viscosity, mPas | 18270 | 17645 | 17350 | 16680 | 15040 | 12850 |
As seen from Table 4, in leaving standstill 80 days, there is not obvious reduction in the apparent viscosity of Gel profile control agent 2; In leaving standstill 100 days, apparent viscosity is higher than 15000mPas, and compared with Gel profile control agent 1, the stability of Gel profile control agent 2 is better.
Embodiment 3
One, the preparation of Gel profile control agent 3
With the gross weight of Gel profile control agent 3 for benchmark, its raw material consists of: allyl group ammonium type hydrophobic associated polymer 0.35%, polymine 0.60%, ammonium persulphate 0.20%, ethanol 0.40%, and surplus is the salt solution of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L.Wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1,300 ten thousand, and degree of hydrolysis is 23-27%, and hydrophobic association group content is 1.8wt%; The relative molecular mass of described polymine is 20,000.
The preparation method of this Gel profile control agent 3 is:
(1) salt solution (ionic concn is considered ionic concn in last obtained Gel profile control agent and prepares) preparation hydrophobic associated polymer mother liquor mass concentration is first used to be 2.0wt%, polymine mother liquor mass concentration is 2.0wt%, respectively slaking 12h under normal temperature;
(2) calculate required for hydrophobic associated polymer mother liquor, polymine mother liquor and preparation mother liquor after the remaining salt solution number that accounts for Gel profile control agent cumulative volume be respectively 17.5 parts, 30 parts and 52.5 parts;
(3) with the gross weight of described Gel profile control agent for benchmark, the ammonium persulphate of 0.20% and the ethanol of 0.40% are dissolved in the salt solution of 52.5 parts by volume, stir;
(4) by the hydrophobic associated polymer mother liquor of 17.5 parts by volume and and the polymine mother liquor of 30 parts by volume join successively in the solution that step (3) obtains, stir, namely obtain freshly prepared Gel profile control agent 3 solution;
(5) solution that step (4) obtains is poured in vial seal;
(6) vial is positioned in the constant temperature oven of 80 DEG C, treats its standing plastic, namely obtain the resistance to high salt of the present embodiment from tack-producing hydrophobic association polymer Gel profile control agent 3.
Two, Gel profile control agent 3 from thickening property
Shown in Fig. 3 be different time of repose time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of this Gel profile control agent recorded under condition.After leaving standstill 20h, gel viscosity starts remarkable rising, shows that now starting gel component crosslinking reaction speed accelerates; After leaving standstill 50h, gel viscosity amplification reduces, and show that now gel component reaction is close to complete, gelation time is 50h, and gel apparent viscosity now reaches 18650mPas; Gel apparent viscosity when leaving standstill 100h is 21660mPas.
Three, the reservoir core plugging performance of Gel profile control agent 3
Shown in table 5 is the sealing characteristics parameter of Gel profile control agent 3 to three kinds of different rate of permeation fill out sand tube rock cores.
The reservoir core plugging performance perameter of table 5 Gel profile control agent 3
| Numbering | 1 | 2 | 3 |
| Core permeability, μm 2 | 4.89 | 1.37 | 0.48 |
| Breakthrough pressure gradient, MPa/m | 24.48 | 24.35 | 27.95 |
| Reservoir core plugging rate, % | 99.05 | 99.34 | 99.87 |
As seen from Table 5, the breakthrough pressure gradient of Gel profile control agent 3, higher than 24MPa/m, to the sealing ratiod of the fill out sand tube rock core of three kinds of rate of permeation ranks all more than 99%, has good reservoir core plugging performance.
Four, the stability of Gel profile control agent 3
Be respectively charged in 6 vials by freshly prepared Gel profile control agent 3 solution that the present embodiment is prepared and seal, the liquor capacity in each vial is 100mL; Vial is positioned in the constant temperature oven of 80 DEG C, takes out when specified time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of Gel profile control agent is tested under condition.Namely shown in table 6 is the viscosity data of Gel profile control agent 3 when leaving standstill different time.
The stability parameter of table 6 Gel profile control agent 3
| Leave standstill number of days, d | 20 | 40 | 60 | 80 | 100 | 150 |
| Apparent viscosity, mPas | 21240 | 19855 | 19540 | 19150 | 18040 | 13070 |
As seen from Table 6, in leaving standstill 80 days, there is not obvious reduction in the apparent viscosity of Gel profile control agent 3; In leaving standstill 100 days, apparent viscosity, higher than 15000mPas, is compared with 2 with Gel profile control agent 1, and the stability of Gel profile control agent 3 is better.
Embodiment 4
One, the preparation of Gel profile control agent 4
With the gross weight of Gel profile control agent 4 for benchmark, its raw material consists of: allyl group ammonium type hydrophobic associated polymer 0.40%, polymine 0.70%, Sodium Persulfate 0.30%, ethanol 0.50%, and surplus is the salt solution of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L.Wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1,300 ten thousand, and degree of hydrolysis is 23-27%, and hydrophobic association group content is 1.8wt%; The relative molecular mass of described polymine is 20,000.
The preparation method of this Gel profile control agent 4 is:
(1) salt solution (ionic concn is considered ionic concn in last obtained Gel profile control agent and prepares) preparation hydrophobic associated polymer mother liquor mass concentration is first used to be 2.0wt%, polymine mother liquor mass concentration is 2.0wt%, respectively slaking 12h under normal temperature;
(2) calculate required for hydrophobic associated polymer mother liquor, polymine mother liquor and preparation mother liquor after the remaining salt solution number that accounts for Gel profile control agent cumulative volume be respectively 20 parts, 35 parts and 45 parts;
(3) with the gross weight of described Gel profile control agent for benchmark, the Sodium Persulfate of 0.30% and the ethanol of 0.50% are dissolved in the salt solution of 45 parts by volume, stir;
(4) by the hydrophobic associated polymer mother liquor of 20 parts by volume and and the polymine mother liquor of 35 parts by volume join successively in the solution that step (3) obtains, stir, namely obtain freshly prepared Gel profile control agent 4 solution;
(5) solution that step (4) obtains is poured in vial seal;
(6) vial is positioned in the constant temperature oven of 80 DEG C, treats its standing plastic, namely obtain the resistance to high salt of the present embodiment from tack-producing hydrophobic association polymer Gel profile control agent 4.
Two, Gel profile control agent 4 from thickening property
Shown in Fig. 4 be different time of repose time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of this Gel profile control agent recorded under condition.After leaving standstill 10h, gel viscosity starts remarkable rising, shows that now starting gel component crosslinking reaction speed accelerates; After leaving standstill 40h, gel viscosity amplification reduces, and show that now gel component reaction is close to complete, gelation time is 40h, and gel apparent viscosity now reaches 20880mPas; Gel apparent viscosity when leaving standstill 100h is 25360mPas.
Three, the reservoir core plugging performance of Gel profile control agent 4
Shown in table 7 is the sealing characteristics parameter of Gel profile control agent 4 to three kinds of different rate of permeation fill out sand tube rock cores.
The reservoir core plugging performance perameter of table 7 Gel profile control agent 4
| Numbering | 1 | 2 | 3 |
| Core permeability, μm 2 | 5.02 | 1.23 | 0.51 |
| Breakthrough pressure gradient, MPa/m | 26.42 | 28.78 | 29.57 |
| Reservoir core plugging rate, % | 99.35 | 99.81 | 99.91 |
As seen from Table 7, the breakthrough pressure gradient of Gel profile control agent 4, higher than 26MPa/m, to the sealing ratiod of the fill out sand tube rock core of three kinds of rate of permeation ranks all more than 99%, has good reservoir core plugging performance.
Four, the stability of Gel profile control agent 4
Be respectively charged in 6 vials by freshly prepared Gel profile control agent 4 solution that the present embodiment is prepared and seal, the liquor capacity in each vial is 100mL; Vial is positioned in the constant temperature oven of 80 DEG C, takes out when specified time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of Gel profile control agent is tested under condition.Namely shown in table 8 is the viscosity data of Gel profile control agent 4 when leaving standstill different time.
The stability parameter of table 8 Gel profile control agent 4
| Leave standstill number of days, d | 20 | 40 | 60 | 80 | 100 | 150 |
| Apparent viscosity, mPas | 24545 | 24080 | 23290 | 22740 | 20050 | 14160 |
As seen from Table 8, in leaving standstill 80 days, there is not obvious reduction in the apparent viscosity of Gel profile control agent 4; In leaving standstill 100 days, apparent viscosity is higher than 15000mPas, and therefore, the stability of Gel profile control agent 4 is better.
Embodiment 5
One, the preparation of Gel profile control agent 5
With the gross weight of Gel profile control agent 5 for benchmark, its raw material consists of: allyl group ammonium type hydrophobic associated polymer 0.45%, polymine 0.80%, ammonium persulphate 0.30%, propyl carbinol 0.40%, and surplus is the salt solution of Na ion concentration 80000mg/L, calcium ion concn 1000mg/L.Wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1,300 ten thousand, and degree of hydrolysis is 23-27%, and hydrophobic association group content is 1.8wt%; The relative molecular mass of described polymine is 20,000.
The preparation method of this Gel profile control agent 5 is:
(1) salt solution (ionic concn is considered ionic concn in last obtained Gel profile control agent and prepares) preparation hydrophobic associated polymer mother liquor mass concentration is first used to be 2.0wt%, polymine mother liquor mass concentration is 2.0wt%, respectively slaking 12h under normal temperature;
(2) calculate required for hydrophobic associated polymer mother liquor, polymine mother liquor and preparation mother liquor after the remaining salt solution number that accounts for Gel profile control agent cumulative volume be respectively 22.5 parts, 40 parts and 37.5 parts;
(3) with the gross weight of described Gel profile control agent for benchmark, the ammonium persulphate of 0.30% and the propyl carbinol of 0.40% are dissolved in the salt solution of 37.5 parts by volume, stir;
(4) by the hydrophobic associated polymer mother liquor of 22.5 parts by volume and and the polymine mother liquor of 40 parts by volume join successively in the solution that step (3) obtains, stir, namely obtain freshly prepared Gel profile control agent 5 solution;
(5) solution that step (4) obtains is poured in vial seal;
(6) vial is positioned in the constant temperature oven of 80 DEG C, treats its standing plastic, namely obtain the resistance to high salt of the present embodiment from tack-producing hydrophobic association polymer Gel profile control agent 5.
Two, Gel profile control agent 5 from thickening property
Shown in Fig. 5 be different time of repose time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of this Gel profile control agent recorded under condition.After leaving standstill 5h, gel viscosity starts remarkable rising, shows that now starting gel component crosslinking reaction speed accelerates; After leaving standstill 30h, gel viscosity amplification reduces, and show that now gel component reaction is close to complete, gelation time is 30h, and gel apparent viscosity now reaches 21950mPas; Gel apparent viscosity when leaving standstill 100h is 27120mPas.
Three, the reservoir core plugging performance of Gel profile control agent 5
Shown in table 9 is the sealing characteristics parameter of Gel profile control agent 5 to three kinds of different rate of permeation fill out sand tube rock cores.
The reservoir core plugging performance perameter of table 9 Gel profile control agent 5
| Numbering | 1 | 2 | 3 |
| Core permeability, μm 2 | 5.56 | 1.39 | 0.60 |
| Breakthrough pressure gradient, MPa/m | 26.98 | 29.39 | 31.45 |
| Reservoir core plugging rate, % | 99.50 | 99.85 | 99.94 |
As seen from Table 9, the breakthrough pressure gradient of Gel profile control agent 5, higher than 26MPa/m, to the sealing ratiod of the fill out sand tube rock core of three kinds of rate of permeation ranks all more than 99.5%, has good reservoir core plugging performance.
Four, the stability of Gel profile control agent 5
Be respectively charged in 6 vials by freshly prepared Gel profile control agent 5 solution that the present embodiment is prepared and seal, the liquor capacity in each vial is 100mL; Vial is positioned in the constant temperature oven of 80 DEG C, takes out when specified time, at 80 DEG C and shearing rate 7.34s
-1the apparent viscosity of Gel profile control agent is tested under condition.Namely shown in table 10 is the viscosity data of Gel profile control agent 5 when leaving standstill different time.
The stability parameter of table 10 Gel profile control agent 5
| Leave standstill number of days, d | 20 | 40 | 60 | 80 | 100 | 150 |
| Apparent viscosity, mPas | 26540 | 25890 | 25320 | 24630 | 21820 | 15810 |
As seen from Table 10, in leaving standstill 100 days, there is not obvious reduction in the apparent viscosity of Gel profile control agent 5; In leaving standstill 150 days, apparent viscosity is higher than 15000mPas, and therefore, the stability of Gel profile control agent 5 is better.
Claims (10)
1. resistance to high salt is from a tack-producing hydrophobic association polymer Gel profile control agent, and with the gross weight of this plugging agent for benchmark, its raw material composition comprises:
Host: hydrophobic associated polymer 0.25-0.45wt%,
Linking agent: polymine 0.40-0.80wt%,
Initiator: persulphate 0.10-0.30wt%,
Properties modifier: low mass molecule alcohol 0.20-0.50wt% and
Salt water surplus.
2. resistance to high salt according to claim 1 is from tack-producing hydrophobic association polymer Gel profile control agent, and wherein, described hydrophobic associated polymer comprises allyl group ammonium type hydrophobic associated polymer.
3. resistance to high salt according to claim 2 is from tack-producing hydrophobic association polymer Gel profile control agent, wherein, the relative molecular mass of described allyl group ammonium type hydrophobic associated polymer is 1200-1500 ten thousand, and degree of hydrolysis is 23-27mol%, and hydrophobic association group content is 1.7-2.1mol%.
4. resistance to high salt according to claim 1 is from tack-producing hydrophobic association polymer Gel profile control agent, and wherein, the relative molecular mass of described polymine is 2-5 ten thousand.
5. resistance to high salt according to claim 1 is from tack-producing hydrophobic association polymer Gel profile control agent, and wherein, described low mass molecule alcohol comprises the combination of one or more in ethanol, propyl alcohol, glycerol and propyl carbinol.
6. resistance to high salt according to claim 1 is from tack-producing hydrophobic association polymer Gel profile control agent, and wherein, described persulphate comprises the combination of one or more in Sodium Persulfate, ammonium persulphate and Potassium Persulphate.
7. resistance to high salt according to claim 1 is from tack-producing hydrophobic association polymer Gel profile control agent, and wherein, described salt solution comprises sodium ion that concentration is 0-100000mg/L, concentration is one or both combination in the calcium ion of 0-1500mg/L.
8. the resistance to high salt described in any one of claim 1-7 is from the preparation method of tack-producing hydrophobic association polymer Gel profile control agent, and it comprises the following steps:
(1) hydrophobic associated polymer mother liquor and polymine mother liquor is prepared;
(2) according to described resistance to high the salt weight percentage of initiator and properties modifier and ionic concn of salt solution in tack-producing hydrophobic association polymer Gel profile control agent, initiator and properties modifier are dissolved in salt solution, obtain a mixed solution A;
(3) according to the weight percentage of described resistance to high salt hydrophobic associated polymer and polymine in tack-producing hydrophobic association polymer Gel profile control agent, the hydrophobic associated polymer mother liquor of aequum and the polymine mother liquor of aequum is added in the mixed solution A that step (2) obtains, stir, obtain a mixing solutions B;
(4) the mixing solutions B that step (3) obtains is placed in encloses container, leaves standstill, after its plastic, obtain described resistance to high salt from tack-producing hydrophobic association polymer Gel profile control agent.
9. preparation method according to claim 8, wherein, the mass concentration of the hydrophobic associated polymer mother liquor in step (1) is 1.0-3.0wt%, and the mass concentration of polymine mother liquor is 1.5-4.0wt%; Preferably, step (1) also comprises: by the hydrophobic associated polymer mother liquor for preparing and polymine mother liquor slaking 10-20h at 10-30 DEG C respectively.
10. preparation method according to claim 8, wherein, the temperature left standstill in step (4) is 70-90 DEG C, and the time is 0-100h.
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| CN106433587A (en) * | 2016-09-18 | 2017-02-22 | 中国石油大学(华东) | Combined 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 |
| CN109251738A (en) * | 2018-10-25 | 2019-01-22 | 中国石油化工股份有限公司 | Sepiolite strengthens hydrophobic associated polymer Gel profile control agent and preparation method thereof |
| CN112442345A (en) * | 2019-08-27 | 2021-03-05 | 中国石油天然气股份有限公司 | Anti-dilution controlled hydrogel system and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350044A (en) * | 2016-07-27 | 2017-01-25 | 大港油田集团有限责任公司 | Low-toxicity environment-friendly polymer crosslinking agent for profile control |
| CN106350044B (en) * | 2016-07-27 | 2019-12-31 | 大港油田集团有限责任公司 | Low-toxicity environment-friendly polymer cross-linking agent for profile control |
| CN106433587A (en) * | 2016-09-18 | 2017-02-22 | 中国石油大学(华东) | Combined 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 |
| CN109251738A (en) * | 2018-10-25 | 2019-01-22 | 中国石油化工股份有限公司 | Sepiolite strengthens hydrophobic associated polymer Gel profile control agent and preparation method thereof |
| CN112442345A (en) * | 2019-08-27 | 2021-03-05 | 中国石油天然气股份有限公司 | Anti-dilution controlled hydrogel system and preparation method and application thereof |
| CN112442345B (en) * | 2019-08-27 | 2023-07-25 | 中国石油天然气股份有限公司 | Anti-dilution hydrogel control system and preparation method and application thereof |
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