CN102191023A - Temporary plugging agent for medium/high-temperature oil-gas reservoir - Google Patents
Temporary plugging agent for medium/high-temperature oil-gas reservoir Download PDFInfo
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Abstract
The invention relates to a temporary plugging agent for a medium/high-temperature (80-100 DEG C) oil-gas reservoir. The temporary plugging agent is prepared from the following components in percentage by mass: 2-20% of acrylamide, 0.02-0.5% of N,N-methylene-bisacrylamide, 0.005-0.03% of polymerization inhibitor, 0.05-0.3% of thickener, 0.005-1.0% of initiator, 0.1-10% of viscosity breaker and the balance of water. The initiator is azobis(isobutylamidine hydrochloride), azodiisopropyl imidazoline or azodiisopropyl imidazoline hydrochloride; and the viscosity breaker is hydrogen peroxide, peracetic acid or peracetate. The temporary plugging agent can form high-strength gel under medium/high-temperature stratum conditions, can gelatinize within the specified time and thoroughly break the viscosity, does not damage the stratum after viscosity breaking, and can adapt to sectionalized reconstruction, repeated reconstruction and turning reconstruction of a long well interval of a medium/high-temperature oil-gas reservoir as well as temporary plugging operation of the well interval and stratum in need of temporary plugging.
Description
Invention field:
The present invention relates to a kind of middle high temperature (80～100 ℃) hydrocarbon-bearing pool and block up the high-strength temporary blocking agent that uses in the operation temporarily.
Background technology:
In the transformation process of horizontal well or long well section straight well and long horizontal traverse well, because the well section is longer, can pass the stratum of different rate of permeation and different extent of injury, whole well section is once transformed the purpose that can not realize effectively transforming reservoir, often need carry out the segmentation transformation to long well section.The machine plugging processing method of conventional bridging plug down and pkr need repeatedly play lower tubular column, and the transformation cycle is long, and operating cost is very high, and has the risk of sand card tubing string.For this reason, need seek a kind of chemical temporary plugging agent, the place ahead or the rear of transforming target well section at need form high-intensity temporary plugging agent frozen glue, that shutoff has been transformed or do not need the well section transformed, behind the pressing crack construction of finishing target well section, temporary plugging agent frozen glue can break glue automatically, the convenient row of returning, thus realize segmentation transformation safely and efficiently.In addition, repeat to transform, turn in the layering treatment measures of transformation, oil and water well, often need carry out temporarily stifled protection operation, also need high strength, reservoir had the temporary plugging agent technology of injury some reservoir positions in hydrocarbon zone.
At the temporary plugging agent Study on Technology, carried out certain research work both at home and abroad.United States Patent (USP) 4137182 adopts polyacrylamide and chromium cross linker formation gel to carry out staged fracturing, injects the stratum and utilizes the automatic aquation of gel to break glue after 24 hours, and the gel compressive strength that this technology forms is low, and broken glue is not thorough, behind the broken glue stratum is had than major injury.
In order to improve injury, require temporary plugging agent can thoroughly break glue to the stratum.United States Patent (USP) 6488091 adopts the polyose polymer to add linking agent in waterfrac treatment and forms gel, and proposition adding ammonium persulphate comes degradation polymer, make brokenly glue more thorough, thereby reduce method to formation damage, but the gel plugging strength that forms still a little less than, be not suitable for being used for the temporarily stifled operation of fracturing process.
In order to improve the shut-off capacity of temporary plugging agent, United States Patent (USP) 6169058 has proposed to adopt suction varicosity particle to be used for the technology of waterfrac treatment, but this technology is difficult to form whole shutoff at horizontal section, is not suitable for the pressure break of lateral segment.In order to satisfy the high plugging strength requirement of pressure break measure to temporary plugging agent, directly to utilize acrylamide monomer solution to inject the stratum post polymerization and form frozen glue, the gel compressive strength that this method forms far beyond crosslinked polymer wants high.The solution that adopts water-soluble monomer such as acrylamide to add initiator in United States Patent (USP) 5335726 directly injects the stratum, aggregates into strong frozen glue under 60 ℃ of formation temperature, has very strong sealing characteristics and voltage endurance capability; United States Patent (USP) 6187839 adopts salts solution, azo class water soluble starter and the monomer solution of high salinity to form high-intensity shutoff.But the shutoff system in these patents can only form high-intensity shutoff in the stratum, and the strong frozen glue system that forms under formation condition can not be broken glue, produces nonvolatil obstruction, therefore can not be used for stifled temporarily operation.
In Chinese patent 99113250.5, the system that has adopted polyacrylamide, magnesium oxide, acrylamide, methylene-bisacrylamide, ammonium persulphate and water to form, under 50 ℃, form gel through polyreaction, the gel that forms comes brokenly glue by the aquation of being heated behind injecting steam, solve temporarily stifled shop problem in the steam stimulation.Because the gel that forms is to come brokenly glue by thermal destruction, this technology only is fit to the temporarily stifled operation of steam treatment oil reservoir.
In Chinese patent 200910086548.1, the employing acrylamide is a monomer, and the persulfuric acid salt has been developed high-intensity temporary plugging agent system for causing gel breaker at middle low-temperature reservoir (40～70 ℃).But, being higher than 80 ℃ middle high-temperature oil reservoir for temperature, the broken colloid of the initiation of persulphate type system can decompose fast, and temporary plugging agent can not satisfy the needs of site operation.
At 80～100 ℃ middle high-temperature oil reservoir, most of at present stifled temporarily system of the crosslinked melon glue of organic boron that adopts.United States Patent (USP) 5413178 has compared the influence of the broken colloid of serial redox system to the crosslinked melon glue of boron, and it is better to think that the redox system that adopts Textone and S-WAT is controlled the effect of breaking glue.It is gel breaker that United States Patent (USP) 5950731 adopts the cupric salts and the compound system of chlorite and hypochlorite, and adds the organic amino used as stabilizers and solve brokenly the control problem of glue time, can control brokenly the glue time greater than 4h, break glue after viscosity be lower than 10mPas.But under hot conditions, the temporary plugging agent gelling strength of melon colloid system is lower, and for the intensity that improves system usually adopts the linking agent prescription of high density, this can bring brokenly the residual problem of glue.In United States Patent (USP) 6214773, proposed to add novel titanium salt and the zirconates linking agent improves the method that the crosslinked melon colloid of boron is tied to form glue intensity, but the high problem of breaking glue solution viscosity is still unresolved.
Summary of the invention:
The objective of the invention is provides the high-strength temporary blocking agent that meets the demands for the construction of the temporarily stifled operation of need such as high temperature oil gas reservoir layering in 80～100 ℃ or segmentation.Use this temporary plugging agent to form high-intensity frozen glue under formation condition, shutoff section reservoir carries out the construction operations such as pressure break, acidifying to other objective interval, and temporary plugging agent can break glue automatically behind certain hour, finishes the purpose of temporarily stifled hydrocarbon zone.
The acrylamide monomer solution of higher concentration is under formation temperature, with the water-soluble azo compounds is initiator, form high-intensity frozen glue, divide broken glue under the effect of separating at peroxy oxygen, make the at the appointed time interior broken glue of frozen glue of formation, can satisfy the different requirements of site operation temporarily stifled performance by formula adjustment.
Water-soluble unsaturated monomer described in the temporary plugging agent is an acrylamide.It is the water-soluble unsaturated monomer with very fast propagationrate constant, and the energy polymerization forms the polymkeric substance of higher molecular weight, and the frozen glue that polymerization obtains has higher shut-off capacity.The general working concentration of acrylamide monomer is 2～20% in the temporary plugging agent prescription, and optimal concentration is 3～10%.
Linking agent described in the temporary plugging agent is N, and N-methylene radical acrylamide can form the polymkeric substance of crosslinking structure with the acrylamide monomer copolymerization, can increase the intensity of frozen glue.The general working concentration of linking agent is 0.02～0.5% in the temporary plugging agent prescription, and optimizing concentration is 0.05%.
Under hot conditions, acrylamide monomer can become glue by rapid polymerization, therefore adds stopper and control gelation time in the temporary plugging agent prescription.Stopper described in the temporary plugging agent is a phenolic compound, includes but not limited to Resorcinol, to methylol methyl-phenoxide and tert-butyl catechol.The general working concentration of stopper is 0～0.1%, and optimal concentration is 0.005～0.03%.
In the temporary plugging agent formula system, add the viscosity that viscosifying agent can be adjusted temporary plugging agent, to adapt to of the requirement of different rate of permeation formation conditions to injection system viscosity.Viscosifying agent described in the temporary plugging agent comprises xanthan gum, Natvosol, melon glue and partially hydrolyzed polyacrylamide.The general working concentration of viscosifying agent is 0～1.0%, and optimal concentration is between 0.05～0.3%, and the temporarily stifled system for preparing viscosity at the beginning is 1～300mPa.s (170s
-1), be preferably 15-60mPa.s (170s
-1).
In the temporary plugging agent formula system, add the water-soluble azo compounds and make initiator, polymerizing acrylamide triggered under hot conditions, form high-intensity frozen glue, can stop of the quick degraded of oxidized form gel breaker to frozen glue, prolong the broken glue time.Initiator described in the temporary plugging agent is the water-soluble azo compounds, includes but not limited to that azo two isobutyls narrow hydrochloride (AIBA), azo di-isopropyl tetrahydroglyoxaline (AIP) and azo di-isopropyl imidazoline salt hydrochlorate (AIBI).The general working concentration of initiator is 0.005～1.0%, and optimal concentration is 0.05～0.3%.
Add water-soluble peroxide and make gel breaker in the temporary plugging agent formula system, water-soluble peroxide decomposition rate under hot conditions is steady, can better control brokenly the glue time.Gel breaker described in the temporary plugging agent is a water-soluble peroxide, includes but not limited to hydrogen peroxide, peroxidation acetate and peroxidation acetate.The general working concentration of gel breaker is 0.1～10%, and optimal concentration is 0.15～3%.
The preparation and the application method of this high-strength temporary blocking agent are as follows:
1, under normal temperature condition, acrylamide, methylene-bisacrylamide, stopper are added to the water, be stirred to dissolving fully;
2, viscosifying agent is added in the above-mentioned solution for preparing, after being stirred to viscosifying agent and dissolving fully, adds initiator again, gel breaker is stirred to dissolving fully, promptly is mixed with the high temperature resistance and high strength temporary plugging agent.
3, the high temperature resistance and high strength temporary plugging agent for preparing is injected into pit shaft with volume pump from well head, replaces it to objective interval with displacing liquid, leave standstill the specified time after, carry out follow-up construction operation, and then leave standstill the specified time, treat the row of returning behind the broken glue of temporary plugging agent.
Because the rate of decomposition of initiator, gel breaker is subjected to Temperature Influence very big, therefore the temporary plugging agent of above-mentioned prescription has certain requirement to reservoir temperature, and suitable formation temperature is between 80～100 ℃, and optimum formation temperature is between 85～95 ℃.
The invention effect:
Temporary plugging agent of the present invention has excellent sealing characteristics, and gelation time can be controlled at 30～120min under formation temperature (80～100 ℃), compressive strength height behind the one-tenth glue, and the broken glue time can be controlled at 5h～2d, and broken glue is thorough.Behind the broken glue of temporary plugging agent the stratum is not had injury, stifled temporarily performance can satisfy the requirement of site operation, can improve fracturing effect significantly behind the use temporary plugging agent, saves the working cycle of layering or staged fracturing, has vast market prospect.
Embodiment:
Embodiment 1:
At ambient temperature, take by weighing 80g water in beaker, order adds 3g acrylamide, 0.05gN again, and N-methylene-bisacrylamide and 0.005g Resorcinol are stirred to dissolving fully, add the 0.3g xanthan gum then, be stirred to dissolving fully, add 0.1g azo two isobutyls again and narrow hydrochloride (AIBA) and 0.5g superoxol (30%), adding water is 100g to gross weight, be stirred to dissolving fully, promptly obtain temporary plugging agent.With Brookfield viscometer at 170s
-1Following measure the temporary plugging agent initial viscosity prepare after, temporary plugging agent is put into 90 ℃ of baking ovens, observes to aggregate into and freeze the gelationus time (gelation time) and broken glue is the time (broken glue time) of clear liquid, and the measurement breaking glue solution is at 170s
-1Under viscosity.The results are shown in Table 1.
Table 1 xanthan gum is as the temporary plugging agent prescription and the performance (90 ℃) of tackifier
| Acrylamide | N,N methylene bis acrylamide | Resorcinol | Xanthan gum | Azo two isobutyls are narrowed hydrochloride | Superoxol (30%) | Initial viscosity mPa.s | Gelation time min | Broken glue time h | Breaking glue solution viscosity mPa.s |
| 3g | 0.05g | 0.005g | 0.3g | 0.1g | 0.5 | 54 | 50 | 24 | 1.2 |
Embodiment 2:
At ambient temperature, take by weighing 80g water in beaker, order adds 10g acrylamide, 0.05g N again, N-methylene-bisacrylamide, 0.03g are stirred to dissolving fully after to the methylol methyl-phenoxide, add the 0.1g partially hydrolyzed polyacrylamide then, be stirred to dissolving fully after, add 0.2g azo di-isopropyl tetrahydroglyoxaline and 5g superoxol (30%), adding water is 100g to gross weight, and is stirred to dissolving fully, promptly obtains temporary plugging agent.With Brookfield viscometer at 170s
-1Following measure the temporary plugging agent initial viscosity prepare after, temporary plugging agent is put into 95 ℃ of baking ovens, observes to aggregate into and freeze the gelationus time (gelation time) and broken glue is the time (broken glue time) of clear liquid, and the measurement breaking glue solution is at 170s
-1Under viscosity.The results are shown in Table 2.
Table 2 partially hydrolyzed polyacrylamide is as the temporary plugging agent prescription and the performance (95 ℃) of tackifier
| Acrylamide | N,N methylene bis acrylamide | MEHQ | Partially hydrolyzed polyacrylamide | Azo di-isopropyl tetrahydroglyoxaline | Superoxol (30%) | Initial viscosity mPa.s | Gelation time min | Broken glue time h | Breaking glue solution viscosity mPa.s |
| 10g | 0.05g | 0.03g | 0.1g | 0.2g | 5g | 15 | 55 | 16 | 1.4 |
Embodiment 3:
At ambient temperature, take by weighing 80g water in beaker, order adds 6g acrylamide, 0.05gN again, be stirred to fully dissolving behind N-methylene-bisacrylamide, the 0.02g tert-butyl catechol, add 0.2g melon glue then, be stirred to dissolving fully after, add 0.3g azo di-isopropyl imidazoline salt hydrochlorate and 10g superoxol (30%), adding water again is 100g to gross weight, and is stirred to dissolving fully, promptly obtains temporary plugging agent.With Brookfield viscometer at 170s
-1Following measure the temporary plugging agent initial viscosity prepare after, temporary plugging agent is put into 85 ℃ of baking ovens, observes to aggregate into and freeze the gelationus time (gelation time) and broken glue is the time (broken glue time) of clear liquid, and the measurement breaking glue solution is at 170s
-1Under viscosity.The results are shown in Table 3.
Table 3 melon glue is as the temporary plugging agent prescription and the performance (85 ℃) of tackifier
| Acrylamide | N,N methylene bis acrylamide | Tert-butyl catechol | Melon glue | Azo di-isopropyl imidazoline salt hydrochlorate | Superoxol (30%) | Initial viscosity mPa.s | Gelation time min | Broken glue time h | Breaking glue solution viscosity mPa.s |
| 6g | 0.05g | 0.02g | 0.2g | 0.3g | 10g | 24 | 70 | 18 | 1.3 |
Embodiment 4:
At ambient temperature, take by weighing 80g water in beaker, order adds 6g acrylamide, 0.05gN again, be stirred to fully dissolving behind N-methylene-bisacrylamide, the 0.01g Resorcinol, add the 0.2g Natvosol then, be stirred to dissolving fully after, add 0.2g azo di-isopropyl imidazoline salt hydrochlorate and 5g superoxol (30%), adding water again is 100g to gross weight, and is stirred to dissolving fully, promptly obtains temporary plugging agent.With Brookfield viscometer at 170s
-1Following measure the temporary plugging agent initial viscosity prepare after, temporary plugging agent is put into 85 ℃ of baking ovens, observes to aggregate into and freeze the gelationus time (gelation time) and broken glue is the time (broken glue time) of clear liquid, and the measurement breaking glue solution is at 170s
-1Under viscosity.The results are shown in Table 4.
Table 4 Natvosol is as the temporary plugging agent prescription and the performance (85 ℃) of tackifier
| Acrylamide | N,N methylene bis acrylamide | Resorcinol | Natvosol | Azo di-isopropyl imidazoline salt hydrochlorate | Superoxol (30%) | Initial viscosity mPa.s | Gelation time min | Broken glue time h | Breaking glue solution viscosity mPa.s |
| 6g | 0.05g | 0.01g | 0.2g | 0.2g | 5g | 20 | 60 | 24 | 1.3 |
Embodiment 5:
The intensity experiment of temporary plugging agent: prepare two segment models, back segment analog casing annular space is placed temporary plugging agent, and the model scale modest ability is 50cm, and external diameter is 3.8cm, and internal diameter is 3.0cm; Leading portion simulation borehole back-up sand section, with the back-up sand of 20-40 order ceramsite propping agent, the model scale modest ability is 50cm, and external diameter is 3.8cm, and perforation diameter is 1.2cm.In baking oven, model is heated to 90 ℃, constant temperature 2h.Then, inject and press the temporary plugging agent solution of table 1 formulated, temporary plugging agent slug length 50cm, water replaces to the borehole position, close 2h at 90 ℃ of following constant temperature and become glue, inject fracturing liquid then under pump speed 15mL/min condition, the record cast pressure at two ends is poor, fluid not still when the result shows pressure difference 18MPa, calculate the temporary plugging agent shutoff after compressive strength greater than 36MPa/m.Continue to close the broken glue of 2d, infusion fracturing liquid then, observing effluent liquid is limpid breaking glue solution, recording viscosity is 1.2mPa.s, takes model apart and observes, the broken fully glue of temporary plugging agent.
Claims (1)
1. temporary plugging agent that is used for the high temperature oil gas reservoir, middle high temperature is 80～100 ℃; It is characterized in that: by acrylamide, N, N-methylene-bisacrylamide, stopper, viscosifying agent, initiator, gel breaker and water are formed, mass percent respectively be 2～20%, 0.02～0.5%, 0.005～0.03,0.05～0.3%, 0.005～1.0%, 0.1～10% and surplus be water;
Described viscosifying agent is xanthan gum, Natvosol, melon glue or partially hydrolyzed polyacrylamide;
Described stopper is Resorcinol, to methylol methyl-phenoxide or tert-butyl catechol;
Described initiator is that azo two isobutyls are narrowed hydrochloride, azo di-isopropyl tetrahydroglyoxaline or azo di-isopropyl imidazoline salt hydrochlorate;
Described gel breaker is hydrogen peroxide, peroxidation acetate or peroxidation acetate.
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