CN109749729A - A kind of blistering cleanup additive and preparation method thereof - Google Patents
A kind of blistering cleanup additive and preparation method thereof Download PDFInfo
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- CN109749729A CN109749729A CN201711080793.2A CN201711080793A CN109749729A CN 109749729 A CN109749729 A CN 109749729A CN 201711080793 A CN201711080793 A CN 201711080793A CN 109749729 A CN109749729 A CN 109749729A
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Abstract
The present invention relates to a kind of blistering cleanup additives and preparation method thereof, belong to oil-gas mining technical field.Blistering cleanup additive of the invention, consist of the following mass percentage components: cationic surfactant 5~15%, nonionic surfactant 0~15%, aoxidize amine amphoteric surfactant 5~20%, fluorocarbon surfactant 0.1~3%, auxiliary agent 0~20%, foam stabilizer 5~12%, surplus are water.Blistering cleanup additive of the invention has excellent frothing capacity, salt resistance, condensate oil performance good, and stability is good in 25% hydrochloric acid；The coordination synergistic effect between surfactant is made full use of, cleanup additive and foaming agent are combined together, a kind of single dose is provided simultaneously with the function of blistering and the row of helping, reduce auxiliary agent type, incompatible risk between reduction single dose, for reducing cost, reinforcing effect is of great significance.
Description
Technical field
The present invention relates to a kind of blistering cleanup additives and preparation method thereof, belong to oil-gas mining technical field.
Background technique
In the recovery process of dense carbonate, since reservoir has, rock core densification, low hole, hypotonic, strata pressure is low
The characteristics of, common acids acid fracturing, fore negative bed, multistage injection acid fracturing and compound plus sand acid fracturing method are generallyd use to reservoir
It is transformed, to realize carbonate reservoir Depth Acid Fracturing, forms stable oil gas flow channel, be finally reached volume increase purpose.
But enter reservoir using fracturing fluid, acid solution during acid fracturing, after fine and close ultra-permeable reservior, by
In stratum energy deficiency, there are the effect of serious Spontaneous capillary imbibition, breaking glue solution/acid solution raffinate of fracturing fluid is all under field conditions (factors)
It is difficult to the row of returning, therefore, cleanup additive and foaming agent are added simultaneously in most of densification low permeability reservoir fracturing fluid/acid solutions.Addition helps row
Agent reduces hollow billet resistance primarily to reduction breaking glue solution surface and interface tension；Be added foaming agent while generally can with fluid injection nitrogen,
Class A foam A working solution system is formed, fluid column static pressure is on the one hand reduced, on the one hand reduces leak-off, while supplementing stratum energy, promote
Into the row of returning.
By years of researches application, foaming agent, cleanup additive type are abundant currently on the market, function admirable.Foaming agent master
It to be made of surfactant-based foaming agent and foam stabilizer；Cleanup additive is mainly made of surfactant, cosolvent.The two is main
Ingredient is surfactant, to reduce cost, gives full play to the compounding effect of two kinds of single doses, it is necessary to provide one kind and have both
The compound blistering cleanup additive of row function is steeped and helped, to reduce cost, improves performance.Such as the China of Patent No. CN106479473
Blistering cleanup additive disclosed in patent text for gas well is by sodium sulfate of polyethenoxy ether of fatty alcohol, dodecyl benzene sulfonic acid
The nonionic surfactants such as the anionic surfactants such as sodium, lauryl sodium sulfate and alkyl polyglycoside, betaines two
Property surfactant amine oxide or alkylolamides class foam stabilizer, auxiliary agent and water composition is added, used auxiliary agent is ethyl alcohol, second
Glycol, butanediol or isopropanol, the blistering cleanup additive mainly for pressing crack construction well, do not hand in acid fracturing/acidizing treatment with
Acid and acid solution other additive compatibility performances.The Chinese invention patent that Authorization Notice No. is 101538462B discloses a kind of oil well and helps
Agent is arranged, helps row, weight percentage of each component applied to the raffinate after oilfield acid fracturing are as follows: dodecyl dimethyl benzyl
Ammonium chloride industrial goods: 7.5~13.5%；Fatty alcohol polyoxyethylene ether, JFC-4 industrial goods: 2~3.5%；Polyxyethylated alcohol
Ether -8JFC industrial goods: 25~34%；Fatty alcohol polyoxyethylene ether, JCF-6 industrial goods: 3.5~5%；Fluorocarbon surfactant
FN-3 industrial goods: 0.05~0.1%, remaining is water；In oil well acidation, pressure break, in acidifying solution, fracturing fluid be added 1~
1.5%, room temperature stirs evenly, and can play reduces the adhesion strength that flows in reservoir of construction raffinate, accelerate raffinate return row 20~
30 percentage points, but the cleanup additive can only be used separately as cleanup additive, the tables such as fatty alcohol polyoxyethylene ether in cleanup additive
Face activating agent has good foaming effect, but is a lack of foam stabilizer, is only used for playing the work for the row of helping in wellfracturing construction
With, can not foam well to form stable foam and play the role of reduce leak-off.
Summary of the invention
The object of the present invention is to provide a kind of acidification/acid fracturing blisterings for having both foaming effect He the row's of helping effect of low cost
Cleanup additive.
The present invention also provides a kind of preparation methods of above-mentioned blistering cleanup additive.
In order to achieve the goal above, technical solution used by blistering cleanup additive of the invention is:
A kind of blistering cleanup additive, consists of the following mass percentage components: cationic surfactant 5~15%, non-
Ionic surface active agent 0~15%, aoxidizes amine amphoteric surfactant 5~20%, and fluorocarbon surfactant 0.1~3% helps
Agent 0~20%, foam stabilizer 5~12%, surplus are water.
Preferably, the cationic surfactant is zephiran class surfactant, alkyl three
One of ammonio methacrylate class surfactant or any combination.It is further preferred that the alkyldimethylbenzylammonium chlorination
Ammonium class surfactant is C12~C18One kind or any combination of zephiran, the alkyl trimethyl chlorine
Change ammonium class surfactant is C12~C18One of alkyl trimethyl ammonium chloride or any combination.
Preferably, the nonionic surfactant is fatty alcohol polyoxyethylene ether, appointing in alkyl phenol polyoxyethylene ether
It anticipates one kind.
Preferably, the oxidation amine amphoteric surfactant is alkyl dimethyl amine oxide, cocamidopropyl propyl amide oxidation
One of amine or any combination.The alkyl dimethyl amine oxide is C12~C18Alkyl dimethyl amine oxide.Aoxidize amine two
Property surfactant can be compounded well with cationic surfactant and nonionic surfactant, reduce surface tension,
Have the effect of foaming and foam stabilizing in blistering cleanup additive concurrently.
Preferably, the fluorocarbon surfactant is perfluoroalkyl ethers quaternary ammonium salt cationic fluorocarbon surfactant, ethoxy
One of base class non-ion fluorin carbon surface active agent or any combination.
Preferably, the auxiliary agent is C2~C7One of low mass molecule alcohol or any combination.Low mass molecule alcohol can be common with water
As the solvent of blistering cleanup additive, in addition the volatility of low mass molecule alcohol facilitates the row of returning of fracturing fluid.The auxiliary agent be ethylene glycol,
At least one of glycerine.
Preferably, the foam stabilizer is one of polypeptide and polyacrylamide or any combination.Polypeptide and polyacrylamide
Amine is cation or non ionic polymer organic matter, can be good at compounding and being somebody's turn to do with the surface-active agent in blistering cleanup additive
Substance can be improved the viscosity of foam, reduce bubble mobility, have preferable steady row's effect.
In above-mentioned composition, alkyl is comprising calibration carbon atom range in straight chain, branch and the alkyl base with cyclic structure
Group, alkyl can be replaced by one or more halogens, alkyl, alkoxy, it is preferred that alkyl is unsubstituted.
Technical solution used by the preparation method of blistering cleanup additive of the invention are as follows:
The preparation method of above-mentioned blistering cleanup additive, comprising the following steps: each component for taking formula ratio, non-ionic surface is living
Property agent be uniformly mixed with auxiliary agent, fluorocarbon surfactant and cationic surfactant, which is then added, to be uniformly mixed, and adds two
Property surfactant be uniformly mixed, be eventually adding foam stabilizer and water be uniformly mixed to get.
Blistering cleanup additive of the invention in the preparation, can carry out at normal temperature.
Blistering cleanup additive of the invention concrete composition and is matched suitable for fine and close oil-gas reservoir acid fracturing/acidification working solution system
Than should be depending on the conditions such as reservoir temperature, salinity.In practical application, (accounting for acid fracturing/acidification working solution matter according to 0.3~1%
Measure percentage) ratio, in acid fracturing/acidification working solution be added blistering cleanup additive.
Blistering cleanup additive of the invention makes full use of the coordination synergistic effect between surfactant, by cleanup additive and foaming agent
It is combined together, a kind of single dose is provided simultaneously with the function of blistering and the row of helping, and reduces auxiliary agent type, reduces incompatible between single dose
Risk is suitable for acid fracturing/acidizing treatment, and for reducing cost, reinforcing effect is of great significance.
Compared with prior art, blistering cleanup additive of the invention has excellent frothing capacity, salt resistance, condensate oil performance
Good, stability is good in 25% hydrochloric acid；The surface of aqueous solution containing blistering cleanup additive 0.3% (mass percent) of the invention
Tension is 22.1mN/m, and interfacial tension 0.4mN/m, the row's of helping performance is good, returns row conducive to working solution.
Specific embodiment
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 8%, non-
Ionic surface active agent 2% aoxidizes amine amphoteric surfactant 10%；Fluorocarbon surfactant 1%, auxiliary agent 15%, foam stabilizing
Agent 7%, surplus are water；Cationic surfactant is dodecyl benzyl dimethyl ammonium chloride, and nonionic surfactant is
C14Fatty alcohol polyoxyethylene ether, oxidation amine amphoteric surfactant are dodecyldimethylamine oxide, fluoro-carbon surface active
Agent is perfluoroalkyl ethers quaternary ammonium salt cationic fluorocarbon surfactant, and auxiliary agent is ethylene glycol, and foam stabilizer is polypeptide.
The preparation method of the blistering cleanup additive of the present embodiment, comprising the following steps: each component for taking formula ratio, by nonionic
Surfactant is mixed with auxiliary agent, is stirred at room temperature to being uniformly dissolved, and fluorocarbon surfactant and cation form is then added
Face activating agent, stirs evenly, and adds amphoteric surfactant, stirs evenly, and is eventually adding foam stabilizer and water, stirs evenly,
To obtain the final product.
Embodiment 2
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 8%, non-
Ionic surface active agent 5% aoxidizes amine amphoteric surfactant 15%；Fluorocarbon surfactant 0.5% is auxiliary agent 20%, steady
Infusion 6%, surplus are water；Cationic surfactant is stearyl dimethyl benzyl ammonium chloride, nonionic surfactant
For alkyl phenol polyoxyethylene ether op-10, oxidation amine amphoteric surfactant is octadecyl dimethyl amine oxide, fluorocarbon surface
Activating agent is perfluoroalkyl ethers quaternary ammonium salt cationic fluorocarbon surfactant, and auxiliary agent is ethylene glycol, and foam stabilizer is polypeptide.
The preparation method is the same as that of Example 1 for the blistering cleanup additive of the present embodiment.
Embodiment 3
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 8%, non-
Ionic surface active agent 5% aoxidizes amine amphoteric surfactant 12%；Fluorocarbon surfactant 3%, auxiliary agent 18%, foam stabilizing
Agent 5%, surplus are water；Cationic surfactant is dodecyl benzyl dimethyl ammonium chloride, and nonionic surfactant is
Alkyl phenol polyoxyethylene ether op-10, oxidation amine amphoteric surfactant are octadecyl dimethyl amine oxide, and fluorocarbon surface is living
Property agent be the non-ionic fluorocarbon surfactant of ethoxy base class, auxiliary agent is glycerine, and foam stabilizer is polyacrylamide.
The preparation method is the same as that of Example 1 for the blistering cleanup additive of the present embodiment.
Embodiment 4
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 5%, non-
Ionic surface active agent 15% aoxidizes amine amphoteric surfactant 20%；Fluorocarbon surfactant 2.5%, foam stabilizer 12%,
Surplus is water；The cationic surfactant is dodecyl benzyl dimethyl ammonium chloride, the nonionic surfactant
For alkyl phenol polyoxyethylene ether op-10, the oxidation amine amphoteric surfactant is octadecyl dimethyl amine oxide, described
Fluorocarbon surfactant is the non-ionic fluorocarbon surfactant of ethoxy base class, and foam stabilizer is polypeptide.
The preparation method of the blistering cleanup additive of the present embodiment, comprising the following steps: each component for taking formula ratio, in nonionic
Fluorocarbon surfactant and cationic surfactant are added in surfactant, stirs evenly, adds amophoteric surface active
Agent stirs evenly, and is eventually adding foam stabilizer and water, stir evenly to get.
Embodiment 5
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 15%,
Aoxidize amine amphoteric surfactant 7%；Fluorocarbon surfactant 2%, auxiliary agent 10%, foam stabilizer 10%, surplus is water；Sun from
Sub- surfactant is octadecyltrimethylammonium chloride, aoxidizes amine amphoteric surfactant as dodecyl dimethyl oxidation
Amine, fluorocarbon surfactant are the non-ionic fluorocarbon surfactant of ethoxy base class, and auxiliary agent is glycerine, and foam stabilizer is polypeptide.
The preparation method of the blistering cleanup additive of the present embodiment, comprising the following steps: each component for taking formula ratio, in auxiliary agent
Fluorocarbon surfactant and cationic surfactant is added, stirs evenly, adds amphoteric surfactant, stir evenly,
Be eventually adding foam stabilizer and water, stir evenly to get.
Embodiment 6
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 8%, oxygen
Change amine amphoteric surfactant 5%；Fluorocarbon surfactant 0.1%, foam stabilizer 5%, surplus are water；Cation surface activating
Agent is dodecyl benzyl dimethyl ammonium chloride, and oxidation amine amphoteric surfactant is cocamidopropyl propyl amide amine oxide, fluorine carbon
Surfactant is the non-ionic fluorocarbon surfactant of ethoxy base class, and foam stabilizer is polypeptide.
The preparation method of the blistering cleanup additive of the present embodiment, comprising the following steps: each component for taking formula ratio, by fluorine carbon table
After face activating agent and cationic surfactant mixing, stirs evenly, add amphoteric surfactant, stir evenly, finally
Foam stabilizer and water is added, stir evenly to get.
Embodiment 7
The blistering cleanup additive of the present embodiment consists of the following mass percentage components: cationic surfactant 10%,
Non-ionic surface active 10% aoxidizes amine amphoteric surfactant 5%；Fluorocarbon surfactant 3%, auxiliary agent 5%, foam stabilizer
9%, surplus is water；Cationic surfactant is dodecyl benzyl dimethyl ammonium chloride and octadecyl trimethyl chlorination
The mass ratio of ammonium, dodecyl benzyl dimethyl ammonium chloride and octadecyltrimethylammonium chloride is 2:1；Non-ionic surface active
Agent is alkyl phenol polyoxyethylene ether op-10 and C14Fatty alcohol polyoxyethylene ether；Alkyl phenol polyoxyethylene ether op-10 and C14Fat
The mass ratio of alcohol polyoxyethylene ether is 1:1；Aoxidizing amine amphoteric surfactant is octadecyl dimethyl amine oxide and cocounut oil
The mass ratio of amidopropyl amine oxide, octadecyl dimethyl amine oxide and cocamidopropyl propyl amide amine oxide is 1:2；Fluorocarbon surface
Activating agent is the non-ionic fluorocarbon surfactant of ethoxy base class；Auxiliary agent is glycerine and ethylene glycol, and foam stabilizer is polypeptide and gathers
Acrylamide；The mass ratio of polypeptide and polyacrylamide is 1:1.
The preparation method is the same as that of Example 1 for the blistering cleanup additive of the present embodiment.
Experimental example
Blistered respectively to the blistering cleanup additive of Examples 1 to 7 and the row's of helping performance detect, test method according to
" measurement (Ross-Miles method) of detergent foaming power " carries out, and it is that foam partly declines that record foam volume, which drops to the time of half,
Phase；The surface and interface tension of blistering cleanup additive is tested using KRUSS100 surface and interface tensiometer.By commercially available foaming agent and cleanup additive
Frothing capacity and the row's of helping performance and embodiment compare, the same Examples 1 to 7 of performance test methods；Wherein commercially available foaming agent is
The product of the model YFP-1 of Zhengzhou City Xinzheng Mei Jiu Industrial Co., Ltd. production, commercially available cleanup additive are that Zhengzhou City Xinzheng plum is long
The product of the model DL-12 of Industrial Co., Ltd.'s production.
The performance test of the cleanup additive of Examples 1 to 7 and comparative example the results are shown in Table 1.
The performance parameter of the cleanup additive of 1 Examples 1 to 7 of table and comparative example
Note: the concentration in table refers to that blistering cleanup additive accounts for the mass percent of working solution.
The blistering cleanup additive of the embodiment of the present invention 1~7 has compared with commercially available foaming agent, cleanup additive as can be seen from Table 1
There are the function of being individually added into blistering and the row of helping, and definite ingredients, is added in fracturing fluid system relative to two kinds of single doses, avoids and match
The problem of 5 property differences, has saved cost, has improved builder activity.Compared with commercially available foaming agent and cleanup additive, embodiment foaming effect
Fruit is preferable, the foam stabilizing time is longer, can reduce the leak-off of fracturing fluid in the construction process, and table, interfacial tension are lower, reduce
Injury of the fracturing fluid filtrate to reservoir, conducive to the row of returning.
Claims (10)
1. a kind of blistering cleanup additive, it is characterised in that: consist of the following mass percentage components: cationic surfactant 5
~15%, nonionic surfactant 0~15% aoxidizes amine amphoteric surfactant 5~20%, fluorocarbon surfactant
0.1~3%, auxiliary agent 0~20%, foam stabilizer 5~12%, surplus is water.
2. blistering cleanup additive according to claim 1, it is characterised in that: the cationic surfactant is alkyl-dimethyl
One of base benzyl ammonium chloride class surfactant, alkyl trimethyl ammonium chloride class surfactant or any combination.
3. blistering cleanup additive according to claim 2, it is characterised in that: zephiran class surface
Activating agent is C12~C18One kind or any combination of zephiran, the alkyl trimethyl ammonium chloride class table
Face activating agent is C12~C18One of alkyl trimethyl ammonium chloride or any combination.
4. blistering cleanup additive according to claim 1, it is characterised in that: the nonionic surfactant is poly alkyl alcohol
One of ethylene oxide ether, alkyl phenol polyoxyethylene ether or any combination.
5. blistering cleanup additive according to claim 1, it is characterised in that: the oxidation amine amphoteric surfactant is alkane
One of base dimethyl amine, cocamidopropyl propyl amide amine oxide or any combination.
6. blistering cleanup additive according to claim 5, it is characterised in that: the alkyl dimethyl amine oxide is C12~C18Alkane
Base dimethyl amine.
7. blistering cleanup additive according to claim 1, it is characterised in that: the fluorocarbon surfactant is perfluoroalkyl ethers
Any one in quaternary ammonium salt cationic fluorocarbon surfactant, ethoxy base class non-ionic fluorocarbon surfactant.
8. blistering cleanup additive according to claim 1, it is characterised in that: the auxiliary agent is C2~C7Low mass molecule alcohol in
A kind of or any combination.
9. blistering cleanup additive according to claim 1, it is characterised in that: the foam stabilizer is polypeptide, in polyacrylamide
One kind or any combination.
10. a kind of preparation method of blistering cleanup additive as described in claim 1, it is characterised in that: each component of formula ratio is taken,
Nonionic surfactant is uniformly mixed with auxiliary agent, fluorocarbon surfactant and cationic surfactant mixing is then added
Uniformly, amphoteric surfactant is added to be uniformly mixed, be eventually adding foam stabilizer and water be uniformly mixed to get.
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