CN104140801B - A kind of alumina gel profile control agent and preparation method thereof - Google Patents
A kind of alumina gel profile control agent and preparation method thereof Download PDFInfo
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- CN104140801B CN104140801B CN201310523174.1A CN201310523174A CN104140801B CN 104140801 B CN104140801 B CN 104140801B CN 201310523174 A CN201310523174 A CN 201310523174A CN 104140801 B CN104140801 B CN 104140801B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
The present invention relates to a kind of alumina gel profile control agents and preparation method thereof.Its main feature is that using aluminium salt for gel generating agent, it is configured to be suitble to the series of products of different reservoir conditions by adding auxiliary agent and retarder.In hot conditions the alumina gel that chemical reaction generates occurs for system has the function of blocking to high permeability formation, reacts while generating CO2, stratum energy can be supplemented, moreover it is possible to and displacement remaining oil, therefore it has been provided simultaneously with the double action for reconciling and driving.Due to low with base fluid viscosity, there is good injection in hyposmosis high contents of calcium and magnesium oil reservoir；It is adjustable between 70~130 DEG C of 3~192h of condition gelation time；Gel viscosity is adjustable between 390~150000mPas；Plastic process is only influenced by reservoir temperature and the variation of system pH value；It disclosure satisfy that the needs of hyposmosis high temperature and high salt oil deposit deep profile correction.
Description
Technical field
The present invention relates to a kind of alumina gel profile control agents and preparation method thereof, belong to Oilfield Chemicals and oil-gas mining profile control technique
Field.
Background technology
Low-permeability oil deposit has taken on a certain scale, and such target will be more and more from now on, according to incompletely statistics：
It is hypotonic reserves that oil in place about 70% or more is newly visited in China, is mainly distributed on long celebrating, grand celebration, Jilin, Xinjiang, the Central Plains areas Deng You.
In oilfield development process, waterflooding extraction is supplement stratum energy, improves the most economical and effective method of oil recovery factor.Due to
The anisotropism on stratum, often forms high infiltration strip during waterflooding extraction, injection water often along high permeability zone flow and quickly
It being flowed out from oil well, forms inefficient cycle so that produced liquid in oil well moisture content steeply rises, and water logging, waterflood recovery efficiency factor is caused to decline,
Waterflood efficiency is not only seriously affected, but also the protection of the processing and gathering line to production fluid all causes series of negative shadow
It rings, drastically influences development cost.
To solve the above problems, common solution is to implement profile control transfer drive technical finesse.Domestic and international chemical profile control agent
Type it is very much, be broadly divided into three categories：
The first kind is with cement, the inorganic particle class for removing soil as host agent, and since the injection of particle limits, such product is only
It is suitble to middle and high infiltration oil reservoir to use.
Second class is polymer gel profile control agent, wherein most representative is HPAM- high volence metal ions（Such as Al
(III), Cr (III) and Zr (IV) system）With the organic phenolic systems of HPAM-.These are using high molecular polymer as the profile control of host agent
Which kind of cross-linking system no matter agent use due to being limited by host agent heat and salt resistance, due to the limitation of polymer its molecule itself,
High temperature strand is easily broken off, and the term of validity is short, is also only applicable to the oil reservoir that temperature is less than 90 DEG C.
Third class is inorganic gel class, and ZL200910002405.8 discloses a kind of inorganic gel profile control agent, by waterglass
7-8%、CO(NH2)21%-2%, HCL2%-3% and water 80%-90% are mixed, and this inorganic gel profile control agent has resistance to
The performance characteristics of high temperature, high salinity；ZL200410029654.3 discloses a kind of inorganic delay silicic acid gel plugging and profile, by 5
~15% waterglass, 0.1~0.6% ethyl acetate, 0.1~3% acetamide, 0.1~0.3% ethyl alcohol, remaining be
Water mixes, and this system can be not only used for 70 DEG C hereinafter, can more be used to carry out single-fluid process oil-water well at a temperature of 70~110 DEG C
Water plugging and profile controlling.It is this kind of to be precipitated by the inorganic silica gels system that waterglass is host agent due to meeting the i.e. rapid reaction of calcium and magnesium ion,
Nearly well plugging is caused, cannot achieve the injection of large dosage, it is difficult to carry out deep profile correction.ZL200910113623.9 discloses one kind
Delayed precipitation granulated gel profile control agent and its production method, the profile control agent by 5% to 30% iron aluminium metalloid salt, 1% to 10%
Methenamine and the water of surplus are constituted, and the high permeability zone of underground is injected using single-fluid process hybrid mode, makes crow using formation temperature
Lip river tropine gradually resolves into ammonium hydroxide and formaldehyde at high temperature, and ammonium hydroxide generates the precipitations such as aluminium hydroxide with iron aluminium metalloid reactant salt,
Gradually block high permeability zone.But profile control agent gelation time at 80 DEG C is less than 5 hours, as temperature increases gelation time meeting
Become smaller, it is difficult to be applied to higher temperature reservoir condition, and iron aluminium metalloid salt uses concentration in 10-20% in the profile control agent, makes
It is higher with cost.ZL00103532.0 discloses a kind of Propile control agent with delayed cross-linking depth, by anionic polymer, Wu Luotuo
Product, phenol, oxalic acid composition, it is characterized in that formula is by weight：Anion-polyacrylamide, molecular weight>10000000, water
Solution degree 25-30%, methenamine：Phenol：Oxalic acid=0.15-0.5%：0.4-0.8%：0.1-0.3%：0.1-0.2%；Match again by above-mentioned
Square weight ratio is made into the aqueous solution of 0.7-2.5%.The invention is low using concentration, and gelation time and viscosity are higher.But the tune
It cuts open in agent prescription and can not be applied to high temperature containing polyacrylamide（More than 100 DEG C）With high calcium magnesium ion（>2000mg/L）Oil reservoir
Under the conditions of.
Although there are many existing high permeability reservoir profile control transfer drive method, technology is also relatively ripe, due to China Central Plains, newly
The low permeability oil fields such as boundary, triumph have the characteristics that high temperature and high salt, high calcium magnesium ion, have both required blocking agent temperature-resistant anti-salt, anticalcium magnesium,
Simultaneously again must satisfy can injection requirement, prior art bad adaptability.
Invention content
The purpose of the present invention overcome above-mentioned profile control transfer drive system heatproof, salt resistance, anticalcium magnesium and can injection etc. deposit
Defect, a kind of alumina gel profile control agent is provided, the displacement construction of high temperature and high salt, high contents of calcium and magnesium reservoir condition can be met, can be controlled
Make its gelation time and intensity.
Second object of the present invention is to provide a kind of preparation method of alumina gel profile control agent.
The present invention is realized by the following technical programs：A kind of alumina gel profile control agent, by gel generating agent, auxiliary agent delays
Solidifying agent and water are mixed by following dosage：
The mass concentration of each component is respectively：Gel generating agent 2~7%, auxiliary agent 1.5~7%, retarder 0.1~0.2%,
Remaining is water.
The gel generating agent is one or both of alchlor or aluminum sulfate.
The auxiliary agent is CO (NH2)2Or NH4HCO3；
The retarder is one or both of ammonium nitrate or citric acid.
The water is that total salinity is 0~25 × 104Mg/l normal saline solutions.
A kind of preparation method of alumina gel profile control agent, includes the following steps：
（1）Water is first added in the mixing vessel with agitating device, based on gross mass 100%, mass concentration, which is added, is
It is spare to form auxiliary agent for 1.5~7% auxiliary agent, stirring and dissolving；
（2）In step（1）In in obtained auxiliary agent, based on gross mass 100%, the gel life of mass concentration 2~7% is added
It is stirred to all dissolvings to get low to base fluid viscosity at the retarder of agent, 0.1~0.2%, and there are different gelation times simultaneously
With a kind of alumina gel profile control agent of gel strength；
The gel generating agent is one or both of alchlor or aluminum sulfate.
The auxiliary agent is CO (NH2)2Or NH4HCO3。
The retarder is one or both of ammonium nitrate or citric acid.
Beneficial effects of the present invention：It uses using aluminium salt as host agent, alumina gel tune is mixed by adding auxiliary agent and retarder
Agent series formula is driven, system is 70~130 DEG C, salinity≤25 × 104Mg/l reservoir media conditions gelation time 3~
192h, 390~150000mPa.s of gel viscosity, 130 DEG C of condition gel stability times are more than 300 days, and plastic process is only by oil reservoir
The influence of temperature and the variation of system pH value, other conditions are unlimited, and system also there is base fluid viscosity to be less than 1.12mPa.s simultaneously, meet
Calcium ions and magnesium ions do not precipitate, and can effectively solve the injection sex chromosome mosaicism of low-permeability oil deposit.It is also generated while gel generates
CO2, it is a kind of effective oil displacement agent, viscosity of crude can be reduced and make crude oil volume expansion, improve oil displacement efficiency；Alkalescent ammonia
Water is also acted on the organic acid (such as aphthenic acids, asphaltogenic acid) in crude oil, can be with in-situ generation petroleum carboxylate class surface-active
Agent.Therefore it has been provided simultaneously with the double action for reconciling and driving, can be used as high temperature and high salt high contents of calcium and magnesium low-permeability oil deposit in-depth profile control makes
With high-capacity channel can be blocked, moreover it is possible to supplement stratum energy, reach displacement remaining oil and improve recovery ratio purpose.
Description of the drawings：
Attached drawing 1 is the alumina gel profile control agent heat stability testing that the embodiment of the present invention 1 obtains；
Attached drawing 2 is the alumina gel profile control agent rock core injection evaluation that the embodiment of the present invention 1 obtains；
Attached drawing 3 is the plugging effect for the alumina gel profile control agent rock core that the embodiment of the present invention 1 obtains；
Attached drawing 4 is the variation for alumina gel profile control agent reaction pressure in closed rock core that the embodiment of the present invention 1 obtains.
Specific implementation mode：
Technical scheme of the present invention is further described with reference to embodiment.
Embodiment 1
（1）By the CO (NH of 2g2)2It is added to 93g brine（Total salinity 12 × 104Mg/L, calcium 4000mg/L, magnesium
1000mg/L）In, it is spare to form auxiliary agent for stirring and dissolving.
（2）5g crystal aluminum chlorides are added in auxiliary agent, stirs to being completely dissolved, obtains a kind of alumina gel profile control agent.
Above-mentioned alumina gel profile control agent is fitted into 100ml high temperature resistants tool plug glass tube, high temperature pipe is put into difference after sealing
In the insulating box of temperature, generation reacts as follows and generates gel.
Following hydrolysis occurs for auxiliary agent under oil reservoir hot conditions：
CO(NH2)2+3H2O=NH4HCO3+NH3H2O
Gel generating agent occurs to react as follows under weak basic condition：
Al3++3HCO3 -=Al(OH)3+3CO2
Al3++3NH3H2O=Al(OH)3+3NH4 +
Alkalescent ammonium hydroxide reacts as follows with organic acid generation in crude oil：
R-COOH+NH3H2O=R-COONH4+H2O
The gelation time and gel viscosity of different temperatures alumina gel profile control agent, knot are measured using 1 identical method of embodiment
Fruit is as shown in table 1.
1 different temperatures alumina gel profile control agent gelation time of table and gel viscosity
Alumina gel profile control agent prepared by the above description of test present invention increases within the scope of 70~130 DEG C of temperature with temperature,
Gelation time shortens, and the gel viscosity of generation increases.
Embodiment 2
（1）By the NH of 2g4HCO3It is added to 93g brine（Total salinity 12 × 104Mg/L, calcium 4000mg/L, magnesium 1000mg/
L）In, it is spare to form auxiliary agent for stirring and dissolving.
（2）5g crystal aluminum chlorides, 0.1g citric acids are added in auxiliary agent, it is solidifying that a kind of retardation setting type aluminium can be obtained in stirring and dissolving
Glue profile control agent.
Above-mentioned alumina gel profile control agent is sub-packed in heat resisting and pressure resisting steel cylinder, is placed in after sealing in 130 DEG C of insulating boxs, periodically
Gel viscosity is taken out and measures,
Following hydrolysis occurs for auxiliary agent under oil reservoir hot conditions：
Gel generating agent occurs to react as follows under weak basic condition：
Al3++3HCO3 -=Al(OH)3+3CO2
Al3++3NH3H2O=Al(OH)3+3NH4 +
Alkalescent ammonium hydroxide reacts as follows with organic acid generation in crude oil：
R-COOH+NH3H2O=R-COONH4+H2O
As a result show that generated gel maintains a long-term stability under 130 DEG C of high temperature, experimental result is shown in attached drawings 1.
Embodiment 3~10：Step is identical as embodiment 1 or 2, and reactant and dosage are as shown in table 2.
A kind of 2 alumina gel profile control agent reactant of table and consumption proportion embodiment
1~10 gained inorganic aluminum gel profile control agent of the present embodiment is used into cloth rotary viscosity design determining base fluid viscosity, knot
Fruit is shown in Table 3.
1~10 gained inorganic aluminum gel profile control agent of the present embodiment is fitted into 100ml high temperature resistants tool plug glass tube, after sealing
High temperature pipe is put into the electric heating constant-temperature blowing drying box of steady temperature and is reacted, timing, the solution in high temperature pipe are started
By transparent turn in vain to after not flowing, it is considered as and has generated gel, records gelation time at this time and with cloth rotary viscosity design determining
Gel viscosity the results are shown in Table 3.
A kind of 3 alumina gel profile control agent gelation time of table and gel viscosity measure
The alumina gel profile control agent prepared by embodiment 1 is carried out to rock core displacement reality on reservoir physical simulation experimental provision
It tests.It is 130 DEG C that experimental temperature, which is arranged, with total salinity 12 × 104Mg/L, calcium 4000mg/L, magnesium 1000mg/L salt water saturations are driven
It for artificial core, while returning and being depressed into 25MPa, brine and alumina gel profile control agent are injected with identical speed, become by injection pressure
Change and investigates alumina gel profile control agent injection（See attached drawing 2）, by attached drawing 2 as it can be seen that a kind of alumina gel profile control agent that the present invention obtains exists
There is good injection, the reason is that the viscosity of a kind of alumina gel profile control agent and water that the present invention obtains is basic in simulation core
It is identical, therefore it is not injected into resistance, injection pressure will not be made to increase.
The above-mentioned rock core both ends for being filled with alumina gel profile control agent are closed, waits and is coagulated to gel is formed at 130 DEG C, recorded simultaneously
The variation of closed system reaction process system pressure, influence when investigating system reaction to system pressure（As a result see attached drawing 3）.By
Attached drawing 3 with alumina gel profile control agent in high temperature high pressure enclosed rock core as it can be seen that react, system pressure can increase.Analyze reason
It is：Gas is produced in reaction process（Mainly CO2）, except small part is dissolved into solution, what most of gas took up space
Effect makes closed system pressure increase.
Above-mentioned rock core under the conditions of high temperature high pressure enclosed after the completion of reaction is continued to use brine using identical displacement velocity
Reservoir core plugging effect is investigated in displacement（As a result see attached drawing 4）.By attached drawing 4 as it can be seen that the initial water drive 0.06MPa of rock core both ends pressure difference, envelope
Highest 2.18MPa after stifled, through 0.5PV subsequent waterfloodings, pressure difference 1.5MPa.Reservoir core plugging rate 96%.A kind of aluminium that the present invention obtains is solidifying
Glue profile control agent has stronger shut-off capacity after high-temperature and high-pressure conditions plastic to rock core, and abrasion resistance is preferable.
A kind of alumina gel profile control agent of the present invention is glued with base fluid it can be seen from table 1-3 and attached drawing 1-4 embodiments
Spend that low, injection is good, high temperature resistant, salt tolerant and anticalcium magnesium ability are strong, and gelation time and gel strength can adjust as needed
Feature, gel also generate CO while generation2, have the double action for reconciling and driving, disclosure satisfy that hyposmosis high temperature and high salt oil
Hide the needs of deep profile correction.
Comparative example：For the characteristics of the present invention is further explained, by the present invention and ZL200910113623.9（A kind of delay
Precipitate granulated gel profile control agent and its production method）It is compared.Step is identical as embodiment 1 or 2, reactant and dosage and at
Glue time and gel viscosity are as shown in table 4.
4 present invention of table and ZL200910113623.9 comparative situations
By table 4 as it can be seen that a kind of alumina gel profile control agent of the present invention and ZL 200910113623.9（A kind of delayed precipitation particle
Gel profile control agent and its production method）The present invention is can be seen that in high temperature and high salinity condition from gelation time and gelling strength
Under, gelation time is long, and controllable.It is similar or poor in formulation content, gelling strength ratio ZL
200910113623.9 is big, illustrates that gelation time of the present invention is controllable, higher at adhesiveness, can be used in deep profile correction.
Claims (2)
1. a kind of alumina gel profile control agent, it is characterised in that：It is mixed by aluminium salt gel generating agent, auxiliary agent, retarder and water；Respectively
The mass concentration of component is respectively：Aluminium salt gel generating agent 2~7%, auxiliary agent 1.5~7%, retarder 0.1~0.2%, remaining is
Water；
The aluminium salt gel generating agent is one or both of alchlor, aluminum sulfate；
The auxiliary agent is CO (NH2)2Or NH4HCO3；
The retarder is one or both of ammonium nitrate, citric acid.
2. a kind of preparation method of alumina gel profile control agent, it is characterised in that：It is realized using following steps：
1.5~7% auxiliary agent is added to the water by the first step based on gross mass 100%, stirring and dissolving, and it is spare to form auxiliary agent；
2~7% aluminium salt gel generating agent is added in above-mentioned auxiliary agent in second step, 0.1~0.2% retarder is stirred to all molten
Solution；
The aluminium salt gel generating agent is one or both of alchlor, aluminum sulfate；
The auxiliary agent is CO (NH2)2Or NH4HCO3；
The retarder is one or both of ammonium nitrate, citric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300438A (en) * | 2018-02-05 | 2018-07-20 | 中国石油大学(华东) | A kind of inorganic aluminum Gelling Water shutoff Agent |
| CN110317851A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of screening technique for the profile control polymer that auxiliary microorganism drives |
| CN111808590B (en) * | 2020-08-12 | 2022-07-29 | 延安市永科石油工程技术服务有限公司 | Environment-friendly energy-increasing oil and water well blocking remover capable of rapidly reacting at normal temperature |
| CN113234425B (en) * | 2021-04-09 | 2023-02-28 | 中国石油大学(华东) | Composite aluminum gel plugging agent for deep profile control of medium-low permeability oil reservoir and preparation method and application thereof |
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|---|---|---|---|---|
| CN86104614A (en) * | 1985-07-05 | 1987-04-22 | 陶氏化学公司 | Mixed metal layer hydroxide compound-clay adducts as the thickening material of water and other hydrophylic fluids |
| CN1388141A (en) * | 2002-02-25 | 2003-01-01 | 中国石油天然气股份有限公司勘探开发研究院 | Composite metal zwitterion polymer and its prepn and use |
| CN101787268A (en) * | 2009-12-31 | 2010-07-28 | 新疆新易通石油科技有限公司 | Gel profile control agent for delaying generation of precipitation granules and preparation method thereof |
| CN102604609A (en) * | 2012-02-07 | 2012-07-25 | 中国石油天然气股份有限公司 | Different-part cross-linking water shutoff profile control gel and preparation method thereof |
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2013
- 2013-10-29 CN CN201310523174.1A patent/CN104140801B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104614A (en) * | 1985-07-05 | 1987-04-22 | 陶氏化学公司 | Mixed metal layer hydroxide compound-clay adducts as the thickening material of water and other hydrophylic fluids |
| CN1388141A (en) * | 2002-02-25 | 2003-01-01 | 中国石油天然气股份有限公司勘探开发研究院 | Composite metal zwitterion polymer and its prepn and use |
| CN101787268A (en) * | 2009-12-31 | 2010-07-28 | 新疆新易通石油科技有限公司 | Gel profile control agent for delaying generation of precipitation granules and preparation method thereof |
| CN102604609A (en) * | 2012-02-07 | 2012-07-25 | 中国石油天然气股份有限公司 | Different-part cross-linking water shutoff profile control gel and preparation method thereof |
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