CN104788611B - A kind of thickening agent improving recovery ratio acrylamide-2-methyl propane sulfonic containing 2- - Google Patents
A kind of thickening agent improving recovery ratio acrylamide-2-methyl propane sulfonic containing 2- Download PDFInfo
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- CN104788611B CN104788611B CN201510157470.3A CN201510157470A CN104788611B CN 104788611 B CN104788611 B CN 104788611B CN 201510157470 A CN201510157470 A CN 201510157470A CN 104788611 B CN104788611 B CN 104788611B
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Abstract
The present invention relates to a kind of thickening agents for improving the recovery ratio sulfonic acid of dimethyl propylene containing diacrylamine.Mainly solve the problems, such as that existing fracturing fluid gelatinizer swelling time in factorial construction is long and it is more to generate foam.The component and proportion of the thickening agent are as follows by weight percentage: including aqueous phase monomers solution, initiator, oily phase emulsified solution；The aqueous phase monomers solution is the aqueous solution of monomeric acrylic, acrylamide, 2- acrylamide -2- toluenesulfonic acid, potassium hydroxide, and acrylamide: acrylic acid: 2- acrylamide -2- toluenesulfonic acid: potassium hydroxide: clear water: the mass ratio of initiator is 1:0.9:1.25:0.16:2.2:0.01；The oil phase emulsified solution is atoleine, compound emulsifying agent, and wherein compound emulsifying agent is span 80 and soil temperature 60, and the atoleine: span 80: the mass ratio of soil temperature 60 is 73:9:1.The raising recovery ratio thickening agent, in factorial construction, swelling time is short, and it is few to generate foam when preparation, is suitable for large factory pressing crack construction.
Description
Technical field
The present invention relates to thickening agent a kind of in field of oil field oil extraction, especially a kind of raising recovery ratio acryloyl containing 2-
The thickening agent of amine -2- methyl propane sulfonic acid.
Background technique
Batch production pressing crack construction technology has become one of the agent technology of fine and close oil and the exploitation of shale gas economical and effective, is applying
Work scene how to realize fracturing fluid system quickly continuous mixture be factorial construction key technology.
The batch production fracturing fluid system being commonly used is mainly natural plant gum system and powdery polymer system.Natural plant gum
System includes thickening agent, crosslinking agent and other additives.Thickening agent is usually hydroxypropyl modified guanidine glue dry powder, because temperature is different,
Crosslinking agent is organic boron, organic zirconium or borax, under the conditions of 90 DEG C, to guarantee good temperature and shearing sustainability, thickening agent
For concentration generally 0.5% or so, performance meets related water base pressure in SY/T 6376-2008 " fracturing fluid general technical specifications "
Liquid general technology index is split, residue content is in 400mg/L or so.It is formulated as follows:
The demulsification of+0.1% cleanup additive+0.1% of+1% clay stabilizer of+0.2% organic borate cross-linker of 0.5% hydroxypropyl guar
Agent+0.18%pH regulator+0.036%pH adjusts+0.01% ternary complex of+0.05% gel breaker of auxiliary agent
Conventional polymer systems include thickening polymer, crosslinking agent and other additives.Thickening agent is mainly dendritic polymerization
Object, crosslinking agent are inorganic aluminate, and under the conditions of 90 DEG C, to guarantee good temperature and shearing sustainability, the concentration of thickening agent is general
In 0.35-0.40%, it is formulated as follows:
+ 0.1% cleanup additive of+0.3% aluminum crosslinker+0.5-1% clay stabilizer of 0.35-0.40% polymer thickening agent+
+ 0.01% ternary complex of+0.05% gel breaker of 0.1% demulsifier
The thickening agent of this two sets of systems is primarily present following problems in factorial construction: first is that swelling time is long.Thickening
Agent is dry powder, and complete swelling needs 15-40min when preparation, and under the premise of using efficient liquid equipment, highest prepares speed
10m can only be met3/min；Second is that foam is more.System can generate a large amount of foam when high speed is prepared, and frequently occur pump truck evacuation
The situation of feed flow deficiency, it is difficult to meet 12m3The high discharge capacity construction demand of/min or more.
Summary of the invention
The invention reside in solving the problems, such as background technique, and provide a kind of high recovery rate acrylamide containing 2--
The thickening agent of 2- methyl propane sulfonic acid.The thickening agent of raising recovery ratio acrylamide-2-methyl propane sulfonic containing 2- is liquid milk
Liquid, in factorial construction, swelling time is short, and it is few to generate foam when preparation, can satisfy 12m3The high discharge capacity of/min or more is constructed
Demand, while the amide groups that thickening agent itself has has very strong polarity, prevents clay particle expansion migration, has and prevent swollen work
With.
The present invention solves the problems, such as that it can reach by following technical solution: a kind of raising recovery ratio acryloyl containing 2-
The thickening agent of amine -2- methyl propane sulfonic acid, component and proportion are as follows in mass ratio: including aqueous phase monomers solution, initiator, oily phase
Emulsified solution；The aqueous phase monomers solution is monomeric acrylic, acrylamide, 2- acrylamide-2-methyl propane sulfonic, hydroxide
The aqueous solution of potassium, the acrylamide: acrylic acid: 2- acrylamide-2-methyl propane sulfonic: potassium hydroxide: clear water: initiator matter
Amount is than being 1:0.9:1.25:0.16:2.2:0.01；It is described oil phase emulsified solution be atoleine, compound emulsifying agent, it is described compound
Emulsifier is span 80, soil temperature 60, and the atoleine: span 80: 60 mass ratio of soil temperature is 73:9:1.
A kind of preparation method for the thickening agent improving recovery ratio acrylamide-2-methyl propane sulfonic containing 2-, including it is following
Step:
(1), the preparation of aqueous phase monomers solution
The aqueous solution of acrylamide, acrylic acid, 2- acrylamide-2-methyl propane sulfonic and potassium hydroxide is prepared respectively, it is molten
The concentration of liquid is respectively 45%, 40%, 56% and 20%；The potassium persulfate solution of preparation 10% is as initiator；
The aqueous solution of acrylic acid, 2- acrylamide-2-methyl propane sulfonic is mixed, the aqueous solution of potassium hydroxide is added dropwise, it will
It is neutralized to after pH value is 9, then mixes with the aqueous solution of acrylamide, and prepared initiator solution is added dropwise.
In above-mentioned aqueous phase monomers solution, acrylamide: acrylic acid: 2- acrylamide-2-methyl propane sulfonic: potassium hydroxide:
Clear water: initiator quality ratio is 1:0.9:1.25:0.16:2.2:0.01.
(2), the preparation of oily phase emulsified solution
Atoleine, 60 mixed liquor of span 80 and soil temperature, atoleine: span 80: 60 mass ratio of soil temperature are prepared in proportion
For 73:9:1.
(3), polymerization reaction
Under 1000r/min revolving speed, oily phase 20min is stirred, the aqueous phase solution of monomer, side addition are added under 20 DEG C of low temperature
Side leads to high pure nitrogen, after addition, 80 DEG C of reactor constant temperature, reacts after 18-20h up to milky emulsion shape product.
In the polymerization reaction, the mass fraction of aqueous phase solution is 85%, and the mass fraction of oily phase emulsified solution is 15%；
The aqueous phase monomers solution has added within 10min, and it is 99.99% that reaction whole process, which need to be passed through nitrogen gas purity,.
A kind of rapid-dissoved polymer thickening agent of emulsion form provided by the invention is water-soluble hydrophobic association
Object belongs to partially hydrolyzed polyacrylamide (PHPA) and its derivative, with water-soluble biggish monomeric acrylic, acrylamide, 2- propylene
The aqueous solution of amide -2- methyl propane sulfonic acid is dispersed phase, using atoleine as continuous phase, using this disk and soil temperature as Composite Milk
Agent, persulfate are initiator, the super-concentrated inverse emulsion polymerization of termonomer are realized, due to the gel of super-concentrated inverse emulsion
Effect reduces the chance of chain tra nsfer in polymerization process, and reaction process is easy to control, and polymerization speed is high, and polymer molecular weight is big.Cream
There is unique instant property after the product anti-phase of liquid；Amide groups in product is strong absorption base, there is very strong polarity, can be with
Multiple clay particles are adsorbed simultaneously, clay particle can adsorb multiple macromolecular chains simultaneously again, staggeredly mutually adsorbing as a result, shape
At the Structure Network of polymer-clay particle, the adsorbable a large amount of water of amide groups prevents clay particle expansion fortune with extremely strong
Shifting effect；Simultaneously using the absorption polarity of the amide groups in product, the thickening agent can be made to have in the case where not being crosslinked and taken
Sand characteristic is used for pressing crack construction.
The solution rate of the thickening agent of synthesis is speeded with the increase of initiator amount, since initiator concentration becomes larger,
The living radical number for causing monomer polymerization increases, and the free radical into micella increases, and polymer molecular weight becomes smaller, causes molten
Speed is solved to accelerate.
The solid-carrying performance of the thickening agent of synthesis and prevent swollen performance with the ratio of aquation group and adsorption group in monomer
Variation can have a greater change.When aquation group is less, the ionic carboxylic acid group and sulfonic acid group density on side chain are little,
Charge repulsion between polymer chain is smaller, and intermolecular winding power is not strong, and coalescence is easy between clay, causes to prevent swollen performance and take
Sand degradation；On the contrary, absorption point between amide group and clay is few, and the adsorption net of formation is inadequate when adsorption group is less
Densification equally prevents that swollen performance and solid-carrying performance are deteriorated.
The solution rate of the thickening agent of synthesis prevents that swollen and solid-carrying performance is related to emulsifier, the dosage pair of emulsifier
It forms vacuole interface film strength and thickness has a direct impact, when the dosage of emulsifier is small, the emulsifier point of adsorbed on interfaces
Subnumber is few, and the interfacial film of formation is not fine and close, and intensity is small, easily rupturable, prevents latex particle from stablizing in oily phase, the lotion of formation
Unstable, polymerization can not be normally carried out, and dissolubility prevents that swollen performance and solid-carrying performance are deteriorated；When emulsifier is excessive, grease
Boundary layer thickens, and hinders the movement of living radical, causes the polymer thickening agent molecular weight of synthesis low, though solution rate increases
Fastly, but prevent that swollen and solid-carrying performance is deteriorated.
The thickening agent of synthesis prevents that swollen and solid-carrying performance is related to water phase volume fraction.With the increasing of water phase volume fraction
Add, gel effect increases, and the mobility in vacuole reduces, and the migration of monomer is small, and biradical stopping of chain is delayed to react, and generates
The molecular weight of polymer thickening agent become larger, take sand and preventive effect of expansion enhancing；But when the volume fraction of water phase is excessive, due to opposite
Tailing off for emulsifier, is not enough to form micella, takes sand and preventive effect of expansion is deteriorated.
The polymer of synthesis prevents that swollen and solid-carrying performance is related to the pH value of water phase.It must increase with ph value of aqueous phase, thickening agent
Prevent the enhancing of swollen and solid-carrying performance, this is because monomer solution in it is acid when, there are a large amount of carboxylate radical and sulfonate radical, polymerizations
There is also anions on object strand interferes monomer to cause connecing for free radical with chain according to the mutually exclusive principle of homophilic charge
Closely, the polymer molecular weight of synthesis is low.
The polymer of synthesis prevents that swollen and solid-carrying performance is related to monomer concentration.With the increase of monomer concentration, latex
Intragranular viscosity becomes larger, and becomes difficult biradical double-click termination, and the polymer molecular weight of generation becomes larger, and takes sand and preventive effect of expansion increases
By force, when continuing to increase monomer concentration, the density variation of water phase and oily phase is expanded, the locomitivity enhancing of emulsion particle polymerize
Journey is unstable, takes sand and prevents swollen degradation.
In order to guarantee the temperature resistance and salt resistance characteristic of thickening agent, 2- acrylamide -2- first is preferably introduced in the molecular structure
Base propane sulfonic acid, the 2- acrylamide-2-methyl propane sulfonic monomer are conducive to improve the heat and salinity tolerance of the emulsion polymer of synthesis
Property, it is particularly suitable for the fracturing fluid of preparation water high salinity.
The present invention can have the following beneficial effects: the raising recovery ratio acryloyl containing 2- compared with above-mentioned background technique
The thickening agent of amine -2- methyl propane sulfonic acid, thickening agent are liquid emulsion, and swelling time is short, within complete swelling time 2min, are prepared
When generate foam it is few；Thickening agent itself, which has, prevents swollen, demulsification, heatproof and salt-tolerant trait.
Specific embodiment:
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
The synthesis process of liquid polymer thickening agent:
(1), the preparation of aqueous phase monomers solution
The aqueous solution of acrylamide, acrylic acid, 2- acrylamide-2-methyl propane sulfonic and potassium hydroxide is prepared respectively, it is molten
The concentration of liquid is respectively 45%, 40%, 56% and 20%；The potassium persulfate solution of preparation 10% is as initiator.
225g acrylic acid solution is mixed with the aqueous solution of 223g 2- acrylamide-2-methyl propane sulfonic, 80g hydrogen is added dropwise
The aqueous solution of potassium oxide is neutralized to after pH value is 9, then mix with the aqueous solution of 226g acrylamide, and dropwise addition is prepared
10g potassium peroxydisulfate initiator solution.
In above-mentioned aqueous phase solution, acrylamide: acrylic acid: 2- acrylamide-2-methyl propane sulfonic: potassium hydroxide: clear water:
Initiator quality ratio is 1:0.9:1.25:0.16:2.2:0.01.
(2), the preparation of oily phase emulsified solution
It weighs 73g atoleine, 9g span 80,1g soil temperature 60 and prepares mixed liquor.
(3), polymerization reaction
Under 1000r/min revolving speed, 15g oil-phase solution 20min is stirred, is added within 10min under 20 DEG C of low temperature single
The aqueous phase solution 85g of body, leading to purity in addition is 99.99% high pure nitrogen, after addition, 80 DEG C of reactor constant temperature, instead
It answers after 20h up to milky emulsion shape product.
The aqueous solution of product configuration 0.1-1.5% is made, 2min is stirred with 400 revs/min of rate, can complete swelling,
Blistering rate is lower than 10% under 400 revs/min of rate stirring condition.
Claims (2)
1. a kind of preparation method for the thickening agent for improving recovery ratio acrylamide-2-methyl propane sulfonic containing 2-, it is characterised in that:
The following steps are included:
(1), the preparation of aqueous phase monomers solution
The aqueous solution of acrylamide, acrylic acid, 2- acrylamide-2-methyl propane sulfonic and potassium hydroxide is prepared respectively, solution
Concentration is respectively 45%, 40%, 56% and 20%；The potassium persulfate solution of preparation 10% is as initiator；
The aqueous solution of acrylic acid, 2- acrylamide-2-methyl propane sulfonic is mixed, the aqueous solution of potassium hydroxide is added dropwise, it will wherein
It is mixed after being 9 to pH value, then with the aqueous solution of acrylamide, prepared initiator solution is added dropwise；
In above-mentioned aqueous phase monomers solution, acrylamide: acrylic acid: 2- acrylamide-2-methyl propane sulfonic: potassium hydroxide: clear water:
Initiator quality ratio is 1:0.9:1.25:0.16:2.2:0.01；
(2), the preparation of oily phase emulsified solution
Atoleine, span 80 and polysorbate60 mixed liquor, atoleine: span 80: the mass ratio of polysorbate60 are prepared in proportion
For 73:9:1；
(3), polymerization reaction
Under 1000r/min revolving speed, oily phase 20min is stirred, aqueous phase monomers solution is added under 20 DEG C of low temperature, Bian Tonggao is added on side
Pure nitrogen gas after addition, 80 DEG C of reactor constant temperature, reacts after 18-20h up to milky emulsion shape product；
In the polymerization reaction, the mass fraction of aqueous phase monomers solution is 85%, and the mass fraction of oily phase emulsified solution is 15%.
2. a kind of thickening agent for improving recovery ratio acrylamide-2-methyl propane sulfonic containing 2- according to claim 1
Preparation method, it is characterised in that: the aqueous phase monomers solution has added within 10min, and being passed through nitrogen gas purity is 99.99%.
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| CN108329901B (en) * | 2018-01-08 | 2020-10-30 | 中国石油天然气集团公司 | Emulsion type thickening agent for fracturing fluid and preparation method and application thereof |
| CN109456443A (en) * | 2018-10-10 | 2019-03-12 | 黑龙江吉地油田服务股份有限公司 | A kind of functional form polyacrylamide and preparation method thereof |
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| CN103694984A (en) * | 2013-12-20 | 2014-04-02 | 西南石油大学 | Shale gas acid fracturing drag reducer and reparation method thereof |
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2015
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| US3926756A (en) * | 1968-12-06 | 1975-12-16 | Hercules Inc | Process for preparing high molecular-weight, water soluble vinyl polymers by irradiation |
| CN104250341A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfonic acid type polyacrylamide emulsion preparation method |
| CN104448130A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof |
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