CN105368424A - Intercalation delay in-situ polymerization water shutoff gel for high-temperature oil reservoir - Google Patents
Intercalation delay in-situ polymerization water shutoff gel for high-temperature oil reservoir Download PDFInfo
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- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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Abstract
The invention belongs to the field of oilfield chemistry related to the enhanced oil recovery technique, and particularly relates to intercalation delay in-situ polymerization water shutoff gel for a high-temperature oil reservoir. The intercalation delay in-situ polymerization water shutoff gel is prepared from, by mass, 6-8% of host agent, 1-2% of cross-linking agent, 2-8% of intercalation host agent, 0.06-0.1% of initiator, 0.01-2% of gelling regulating agent, and the balance water. The intercalation delay in-situ polymerization water shutoff gel has the advantages that the fast dissolving property of components in the gel system is good, and liquid dosing is convenient; the construction technology is simple, pumpability is high, and injectivity is high; gelling time can be controlled to be 4-30 h at 130 DEG C; long-term stability is high at high temperatures, and synaeresis and strength reduction does not occur on the gel within three months; influence on gelling performance is small, leak-off prevention can be well achieved, and the gel can be used for water shutoff of fractured reservoirs.
Description
Technical field
The invention belongs to the field of oilfield chemistry improved in recovery efficiency technique, particularly relate to a kind of intercalation synthesis for high-temperature oil reservoir and delay polymerization in situ water shutoff gel.
Background technology
Chemical profile control water-plugging technique oil field is applied comparatively ripe " water and oil control ", " water-control oil-increasing " technology, effectively can improve and inject water sweep efficiency, reach the object improving recovery ratio.In chemical profile control plugging agent gel-like plugging agent have shut-off capacity strong, can the advantage such as selective water shut-off, be widely used in profile control and water plugging operation.But, under the condition that reservoir temperature is higher, conventional GPC blocking agent cannot reach the technical requirements of profile control and water plugging operation, for meeting the profile control and water plugging job requirements under high-temperature oil reservoir condition, need the Gelling Plugging Agent that performance is more excellent, large quantity research has been carried out to the Gelling Plugging Agent being applicable to high-temperature oil reservoir both at home and abroad.
(1) polyvinyl alcohol gel rubber system
Polyvinyl alcohol gel rubber system has good heat resistance, and the polyvinyl alcohol using resol as linking agent/phenolic aldehyde gelling system can be used for the water-blocking operation in steam flood oil field.As Hoskin and Shu (1989) adopts concentration to be that the polyvinyl alcohol of 7.5% is as host, adopt concentration be 8% phenols and aldehydes as organic crosslinking agent, prepare Novel polyvinyl alcohol gelling system (USPatent4,859,717), system aging more than 70 skies at 204.4 DEG C only dewater about 5%, and long-term thermal stability is better.But polyvinyl alcohol gel rubber system requires comparatively harsh to pH value condition, need control ph in suitable scope, the too high or too low meeting of pH value causes precipitation or dehydrating phenomena, makes this gelling system apply limited.
(2) partially hydrolyzed polyacrylonitrile gelling system
Partial hydrolysis polypropylene is fine mainly comprises poly hydrolyzate and hydrolyzed polyacrylonitrile ammonium salt, wherein because poly hydrolyzate is easily crosslinked and cheap, apply more, by poly hydrolyzate as host, by resistant to elevated temperatures water shutoff gel can be formed with the crosslinked action of organic crosslinking agent.Xu Xiangyi etc. (1990) adopt the poly hydrolyzate of concentration 4% ~ 6% as host, the formaldehyde of employing concentration 0.4% ~ 0.6% and phenol are as linking agent, adopt concentration be 0.5% ammonium chloride prepared a kind of poly hydrolyzate gel as auxiliary agent, there is not dehydrating phenomena in aging 9 months and 3 months respectively in this gel, have good thermostability at high temperature 130 DEG C and 150 DEG C.Because the gelation time of this system is too fast, be unfavorable for rig-site utilization, therefore Liu Min etc. (1996) have made improvement to this system, adopt hexamethylenetetramine and phenol system as linking agent, gelation time is delayed.But partially hydrolyzed polyacrylonitrile gelling system has certain requirement to Gelation Conditions, pH value is too high or too low all can affect plastic, and therefore the application of this gelling system is restricted.
(3) biopolymer gel system
The kind that biological polymer is applied in petroleum industry is a lot, as xanthocyte gum, Sclerotium gum, melon glue etc., the gel that biological polymer and linking agent are formed has good thermostability, and wherein Sclerotium gum gelling system has better temperature resistant antisalt performance relative to other biological polymer gel cording.The Sclerotium gum gelling system that such as IngebretFjelde (1995) proposes, using Sclerotium gum as host, using dichromate as linking agent, the gel of formation can heatproof more than 100 DEG C.But biopolymerization objects system cost is higher comparatively speaking, gelation time is very fast, cannot be widely used in site operation.
(4) polyacrylamide gel system
The water shutoff gel formed with organic crosslinking agent of the multipolymer that the polymkeric substance of acrylamide and acrylamide and temperature resistance salt tolerant monomer polymerization obtain studies high-temperature oil reservoir water shutoff gel the most widely.The PAtBA/PEI gelling system of the report such as CarlosDeolarteGuerrero (SPE112411), ModestoMercado (SPE121809), JulioEstuardoVasquez (SPE104134) has in the past ten years and is applied to Mexico's south carbonate rock fractured cave type high-temperature oil reservoir more than 100 water-blocking operations, and respond well.PAtBA is the multipolymer of acrylamide and tert-butyl acrylate, gelling system by 7% PAtBA as host, PEI using 0.3% is as linking agent, the gel formed can the high temperature of resistance to 156 DEG C, but this gelling system gelation time is relatively short, and at 120 DEG C, gelation time is only about 5 ~ 8h, and due to PAtBA relative concentration in system higher, make the initial viscosity of system higher, pumping into property is relatively poor.
For water shutoff gel, need sufficiently long gelation time and good long-term thermal stability under the high temperature conditions, and as can be seen from above-mentioned each Gelling Plugging Agent system, Gelation Conditions is harsh, the too fast and long-term thermal stability of gelation time is not enough is under the high temperature conditions the existing subject matter of water shutoff gel, these problems make the performance of existing water shutoff gel cannot meet the application demand of carrying out profile control and water plugging operation in high-temperature oil reservoir, become the technical barrier of high-temperature oil reservoir mid-later development phase " water and oil control ", " water-control oil-increasing ".
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of intercalation synthesis for high-temperature oil reservoir and delays polymerization in situ water shutoff gel, this water shutoff gel defines the three-dimensional space network of lattice intercalation on molecular scale, there is very high final strength and good long-term thermal stability, gelation time can be controlled in 4 ~ 30h under the hot conditions of 130 DEG C, there is the longer infusion time under the high temperature conditions, this gel initial viscosity is low simultaneously, and construction injection is better.This water shutoff gel can overcome the problem that existing water shutoff gel gelation time is too short and long-term thermal stability is not good, is applicable to the water-blocking operation of all types of high-temperature oil reservoir.
In order to solve above-mentioned technical problem, the technical scheme of employing of the present invention is: a kind of intercalation synthesis for high-temperature oil reservoir delays polymerization in situ water shutoff gel, be made up of the component of following mass percent: host 6% ~ 8%, linking agent 1% ~ 2%, intercalation host 2% ~ 8%, initiator 0.06% ~ 0.1%, plastic adjusting control agent 0.01% ~ 2%, all the other are water.
Wherein, as preferred technical scheme, described host is organic monomer acrylamide.
Wherein, as preferred technical scheme, described linking agent is formaldehyde, reactive phenolic resin, Resorcinol, Resorcinol, pyrocatechol, vulkacit H, polymine wherein one or more mixtures.
Wherein, as preferred technical scheme, described intercalation host is one or more mixtures in modified montmorillonite used, kaolinite, diatomite.
Wherein, as preferred technical scheme, described initiator is thermal decomposition initiating or redox system.
Wherein, above-mentioned thermal decomposition initiating is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2-azo diisobutyl amidine dihydrochlorides.
Wherein, above-mentioned redox system is Potassium Persulphate and sodium bisulfite, Potassium Persulphate and tertiary amine monomers N, N-dimethyl β-dimethyl-aminoethylmethacrylate.
Wherein, as preferred technical scheme, described plastic adjusting control agent is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, propylene glycol, glycerol, tetramethylolmethane, n-Octanol, isooctyl alcohol, prenol wherein one or more mixtures.
Beneficial effect of the present invention: in (1) gelling system, various component instantly-soluble is good, dosing is convenient; (2) construction technology is simple, and pumping is good, has good injection; At (3) 130 DEG C, gelation time can be controlled in 4-30h, and final strength reaches range estimation code I level (rigid gel); (4) have good permanent stability under the high temperature conditions, synersis did not occur gel in 3 months and intensity reduces phenomenon; (5) this polymerization in situ gel is carried with the heat and salinity tolerance polymkeric substance of lower concentration, little on gel-forming property impact, better anti-leak-off operation can be played, can be used for fractured reservoir water-blocking operation.
Embodiment
A kind of intercalation synthesis for high-temperature oil reservoir of the present invention delays polymerization in situ water shutoff gel, be made up of the component of following mass percent: host 6% ~ 8%, linking agent 1% ~ 2%, intercalation host 2% ~ 8%, initiator 0.06% ~ 0.1%, plastic adjusting control agent 0.01% ~ 2%, all the other are water.
Wherein, as preferred technical scheme, described host is organic monomer acrylamide.
Wherein, as preferred technical scheme, described linking agent is formaldehyde, reactive phenolic resin, Resorcinol, Resorcinol, pyrocatechol, vulkacit H, polymine wherein one or more mixtures.
Wherein, as preferred technical scheme, described intercalation host is one or more mixtures in modified montmorillonite used, kaolinite, diatomite.
Wherein, as preferred technical scheme, described initiator is thermal decomposition initiating or redox system.
Wherein, above-mentioned thermal decomposition initiating is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2-azo diisobutyl amidine dihydrochlorides.
Wherein, above-mentioned redox system is Potassium Persulphate and sodium bisulfite, Potassium Persulphate and tertiary amine monomers N, N-dimethyl β-dimethyl-aminoethylmethacrylate.
Wherein, as preferred technical scheme, described plastic adjusting control agent is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, propylene glycol, glycerol, tetramethylolmethane, n-Octanol, isooctyl alcohol, prenol wherein one or more mixtures.
The gel-strength (GelStrengthCodes is called for short GSC) that the present invention adopts the people such as Sydansk (1988) to propose is estimated code table (see table 1) and is evaluated gelation time and gelling strength.The intensity of gel is by range estimation phenomenon coded representation, and the gelation time of gel refers generally to system and becomes by solution A the time that flow-gel C experiences.
Table 1 gel-strength range estimation code standard
90 ~ 160 DEG C of baking ovens, visually code methods are put in system sealing the present invention configured, and gelation time controls at 4 ~ 30h by regulating each concentration of component, and final strength is rigid gel I level.And this system configurations is convenient, initial viscosity is low, infusion performance is good, under the effect of initiator and linking agent, polymerization occurs on the spot and form high-strength gel under formation temperature.
For fractured reservoir, system initial viscosity can be increased at the Heat Resistant and Salt Tolerant Polymer by adding lower concentration in aforementioned formula and effectively avoid leak-off or leakage.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention in described scope of embodiments.And the per-cent in each embodiment is mass percent, in proportion the various components of composition gelling system is joined in clear water, stir, do in bottle at 130 DEG C and test, judge gelation time and gelling strength according to range estimation code method.
Embodiment 1
Organic monomer acrylamide total mass concentration is 8%, linking agent (formaldehyde) concentration is 2%, intercalation host (modified montmorillonoid) is 6%, plastic adjusting control agent (ethanol) concentration is 0.8%, initiator (2, two (the 2-methyl-prop amidine) dihydrochloride of 2'-azo) change in concentration scope is 0.06% ~ 0.1%, all the other are water.Plastic situation is in table 2, and its gelation time is between 4 ~ 10h, and final strength is I level, synersis does not occur in 90 days.
Table 2 embodiment 1 plastic situation
| Initiator concentration (%) | 2h | 3h | 4h | 8h | 10h | 1D | 5D | 30D | 90D |
| 0.06 | A | A | A | B | D | I | I | I | I |
| 0.08 | A | A | A | C | G | I | I | I | I |
| 0.1 | A | B | C | H | I | I | I | I | I |
Embodiment 2
Organic monomer acrylamide total mass concentration is 6%, linking agent (reactive phenolic resin) concentration is 1%, intercalation host (kaolin) is 8%, plastic adjusting control agent (methyl alcohol) concentration is 1.5%, initiator (ammonium persulphate) change in concentration scope is 0.06% ~ 0.1%, and all the other are water.Plastic situation is in table 3, and its gelation time is between 16 ~ 24h, and final strength is I level, synersis does not occur in 90 days.
Table 3 embodiment 2 plastic situation
| Initiator concentration (%) | 4h | 8h | 12h | 16h | 20h | 1D | 5D | 30D | 90D |
| 0.06 | A | A | A | A | B | D | I | I | I |
| 0.08 | A | A | A | C | E | H | I | I | I |
| 0.1 | A | A | B | C | H | I | I | I | I |
Embodiment 3
Organic monomer acrylamide total mass concentration is 6%, linking agent (polymine) concentration is 1%, intercalation host (polynite) is 8%, plastic adjusting control agent (methyl alcohol+ethylene glycol, mass ratio 1:2) concentration is 2%, initiator (ammonium persulphate) change in concentration scope is 0.06% ~ 0.1%, and all the other are water.Plastic situation is in table 4, and its gelation time is between 20 ~ 30h, and final strength is I level, synersis does not occur in 90 days.
Table 4 embodiment 3 plastic situation
| Initiator concentration (%) | 10h | 15h | 20h | 30h | 3D | 10D | 30D | 60D | 90D |
| 0.06 | A | A | B | G | I | I | I | I | I |
| 0.08 | A | A | C | H | I | I | I | I | I |
| 0.1 | A | B | E | I | I | I | I | I | I |
Embodiment 4
Organic monomer acrylamide total mass concentration is 8%, linking agent (reactive phenolic resin) concentration is 2%, intercalation host (diatomite) is 8%, plastic adjusting control agent (ethylene glycol) concentration is 1.5%, initiator (ammonium persulphate) change in concentration scope is 0.06% ~ 0.1%, and all the other are water.Plastic situation is in table 5, and its gelation time is between 8 ~ 15h, and final strength is I level, synersis does not occur in 90 days.
Table 5 embodiment 4 plastic situation
Claims (8)
1. the intercalation synthesis for high-temperature oil reservoir delays polymerization in situ water shutoff gel, it is characterized in that, be made up of the component of following mass percent: host 6% ~ 8%, linking agent 1% ~ 2%, intercalation host 2% ~ 8%, initiator 0.06% ~ 0.1%, plastic adjusting control agent 0.01% ~ 2%, all the other are water.
2. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 1 delays polymerization in situ water shutoff gel, it is characterized in that, described host is organic monomer acrylamide.
3. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 1 and 2 delays polymerization in situ water shutoff gel, it is characterized in that, described linking agent is formaldehyde, reactive phenolic resin, Resorcinol, Resorcinol, pyrocatechol, vulkacit H, polymine wherein one or more mixtures.
4. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 3 delays polymerization in situ water shutoff gel, it is characterized in that, described intercalation host is one or more mixtures in modified montmorillonite used, kaolinite, diatomite.
5. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 4 delays polymerization in situ water shutoff gel, it is characterized in that, described initiator is thermal decomposition initiating or redox system.
6. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 5 delays polymerization in situ water shutoff gel, it is characterized in that, described thermal decomposition initiating is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2-azo diisobutyl amidine dihydrochlorides.
7. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 5 delays polymerization in situ water shutoff gel, it is characterized in that, described redox system is Potassium Persulphate and sodium bisulfite, Potassium Persulphate and tertiary amine monomers N, N-dimethyl β-dimethyl-aminoethylmethacrylate.
8. a kind of intercalation synthesis for high-temperature oil reservoir according to claim 6 or 7 delays polymerization in situ water shutoff gel, it is characterized in that, described plastic adjusting control agent is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, propylene glycol, glycerol, tetramethylolmethane, n-Octanol, isooctyl alcohol, prenol wherein one or more mixtures.
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| CN106905939A (en) * | 2017-02-27 | 2017-06-30 | 山东石大油田技术服务股份有限公司 | Superhigh intensity crosslinked gel plugging tune system and its production and use |
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Application publication date: 20160302 |