CN110054727A - A kind of preparation method and device of polyacrylamide nano microballoon - Google Patents
A kind of preparation method and device of polyacrylamide nano microballoon Download PDFInfo
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- CN110054727A CN110054727A CN201910339604.1A CN201910339604A CN110054727A CN 110054727 A CN110054727 A CN 110054727A CN 201910339604 A CN201910339604 A CN 201910339604A CN 110054727 A CN110054727 A CN 110054727A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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Abstract
The invention discloses a kind of preparation method that polyacrylamide nano is slight and devices, acrylamide, crosslinking agent, the liquid material of initiator composition and compressed air are introduced into tubular reactor in a continuous manner, it is generated free radicals so that initiator decomposes at a certain temperature, cause the polymerization reaction of acrylamide, then the logistics comprising polyacrylamide is drawn from tubular reactor, obtains polyacrylamide nano finished microballoon products through collecting.Present invention process is simple, and using the good tubular reactor continuous production of safety, and the polyacrylamide nano microspheres quality prepared is stablized, uniform particle diameter, avoids the excessive kettle in traditional autoclave production technology and sudden and violent poly- phenomenon, improves product quality and production efficiency.
Description
Technical field
The invention belongs to chemical industry synthesis fields, and in particular to a kind of preparation method and dress of polyacrylamide nano microballoon
It sets.
Background technique
Polyacrylamide nano microballoon, using acrylamide as monomer, is handed over added with a small amount of using microemulsion as dispersion
The nanoparticulate polymer with space net structure prepared under conditions of connection agent.After these particles note to stratum,
Partial size is small, solution viscosity is low, is easily accessible earth formation deep, then by water swelling, volume increases, thus can block in stratum
Water flow predominant pathway, improve injection water sweep efficiency.Deep profile correction is carried out with polyacrylamide nano microballoon, for old oil
The water and oil control of hiding and the waterflooding extraction for improving offshore oilfield, LOW PERMEABILITY RESERVOIR and high salinity reservoirs have good effect.
The technique single sintering that polyacrylamide nano microballoon generallys use microemulsion at present obtains, at present mature life
Preparation method is produced mainly include the following types: reversed (micro-) emulsion polymerization, dispersion copolymerization method, precipitation polymerization method, anti-phase suspension are poly-
It is legal.These traditional handicrafts mainly pass through stirred tank as reaction vessel, are mainly characterized by strong using mechanical stirring mode
Change two-phase mixtures, and temperature control is carried out to system and product using the heat-conducting medium in collet.Existing pam microemulsion
Ball synthetic method, number big absolutely pertain only to composition of raw materials, improve production technology without being related to being promoted.As 107868379 A of CN is public
A kind of preparation method of polyacrylamide polymer gel micro-ball is opened, preparation method changes in original production technology link
Composition of raw materials is become, by addition cellulose as crosslinking agent, has formed dual interpenetrating structure in acrylamide gel microballoon, increase
The strong intensity at microsphere expansion initial stage, while realizing gel micro-ball late expansion effect.102181008 A of CN discloses one
For kind with the preparation method of polyacrylamide microsphere water shutoff agent, technique is using four-hole boiling flask simulation process reaction kettle as reaction
Container obtains polyacrylamide microsphere of the partial size between 8~175nm, is somebody's turn to do by the way that initiator polymerization of acrylamide monomer is added
The shortcomings that patent is that microspherulite diameter range is too wide, the grain not being suitable in current " polyacrylamide microsphere profile control agent technical requirements "
Diameter range, simultaneously because partial size otherness causes greatly system unstable, there is lamination in products obtained therefrom standing.CN
106866880 A disclose a kind of method of polydispersion polyacrylamide microsphere system and its preparation, i.e., using similar seed cream
The mode of liquid polymerization is obtained by multistep reaction simultaneously containing nanometer, micron, grade polyacrylamide microsphere, and product is effective
Content is high, but this method need to realize that the reaction time is long by reaction of high order, and process is more, reduces production efficiency and cost.
108314758 A of CN discloses a kind of preparation method of polyacrylamide microsphere lotion, which uses complex emulsifier
With meet initiator system carry out acrylamide polymerization reaction, obtained sub-micron polyacrylamide microsphere good emulsion stability,
Solid content is high.The patent still needs to still reaction, and the initiation system used is oxidationreduction dual initiator, therefore aoxidizes being added
Property initiator before need logical nitrogen protection system, need high shear agitation when reproducibility initiator is added, while also needing strict control
Heating rate≤2 DEG C/min, operation sequence is various and operation requires strictly.
Traditional autoclave production method, there are heat exchange areas in polymerization process, and small, temperature does not accurately control, and stirs
Mixing spatial distribution leads to problems such as particle diameter distribution width wide, and material accelerates polymerization stage after especially polymerization reaction causes,
Because highly exothermic uncontrollable, cause sudden and violent poly- phenomenon to occur, reaction is caused to fail, inventory disposal or even material is agglomerating seizes is stirred
The accident of bar motor damage occurs.Further, since material has certain viscosity, it is easily adhered to reaction kettle surface, for a long time
Easy part autohemagglutination under heating condition, forms thick insoluble gel, which causes product quality to decline if peeling off, if length
Phase is attached to kettle inner surface, easily influences reaction heat transmitting, while equipment cleaning difficulty increases.
Summary of the invention
It is above-mentioned to overcome the purpose of the present invention is to provide the preparation method and device of a kind of polyacrylamide nano microballoon
The technological deficiency of autoclave production method of the existing technology.Present invention process is simple, using the good tubular reactor of safety
Continuous production, and the polymerization rate controllability for preparing polyacrylamide nano microballoon is high, microspherulite diameter distribution is uniform, and can
By adjusting raw material proportioning to control particle size, while gel wall sticking phenomenon common in polymerization reaction is avoided, improved
Product quality and production efficiency, reduce production cost.Preparation facilities structure provided by the invention is simple, and polypropylene may be implemented
The continuous production of amide nanosphere.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of preparation method of polyacrylamide nano microballoon, by acrylamide, crosslinking agent, surfactant and initiator
The liquid material and compressed air of composition are introduced into tubular reactor in a continuous manner, so that decomposition of initiator generates freely
Base causes the polymerization reaction of acrylamide, and the logistics comprising polyacrylamide microsphere is made, then will include polyacrylamide
Logistics is drawn from tubular reactor, obtains polyacrylamide nano finished microballoon products through collecting；
Wherein, the molar ratio of acrylamide and crosslinking agent be 1:(0.001~0.2), initiator amount account for acrylamide with
The 0.01%~0.4% of crosslinking agent gross mass.
Further, compressed air is passed through tubular reactor by way of bubbling, and the liquid flow containing acrylamide is in pipe
By bubble partition at discontinuous segment in road.
Further, compressed air input volume is the 0.1%~1.5% of liquid material input volume, compressed air pump
Entering frequency is 5~40 beats/min.
Further, the outside of the tubular reactor is provided with insulating box；The temperature of insulating box is 50~90 DEG C.
Further, it is 50~600mL/min that liquid material and compressed air, which enter the overall flow rate of tubular reactor,.
Further, the crosslinking agent is N, penylene bismaleimide between N-；The initiator is di-t-butyl
Hydrogen peroxide.
Further, the temperature of polymerization reaction is 55~85 DEG C, and the time is 500~1500s.
A kind of preparation facilities of polyacrylamide nano microballoon, including acrylamide aqueous solution and crosslinking agent mixing kettle, table
Face activating agent mixing kettle, air compressor, acrylamide raw material mixing kettle, bubbler, tubular reactor, insulating box and product are received
Ji Chi；The acrylamide aqueous solution connect acrylamide with the outlet end of crosslinking agent mixing kettle, surfactant mixing kettle
The input end of raw material mixing kettle, the liquid feeding end of the outlet end connection tubular reactor of acrylamide raw material mixing kettle；Compressed air
The input end of the outlet end connection bubbler of machine, the inlet end of the outlet end connection tubular reactor of bubbler, tubular reactor
Discharge end be connected to product collecting pit；The tubular reactor is arranged in insulating box；The acrylamide raw material is mixed
It closes kettle and is provided with initiator feed opening.
It further include two micro- constant-flux pumps for being respectively used to conveying liquid material and compressed air, wherein for conveying liquids
The outlet end of micro- constant-flux pump of material is connected to tubular reactor import, and micro- constant-flux pump outlet end for conveying compressed air connects
To the leading portion of tubular reactor.
The tubular reactor is single hose reactor, and the internal diameter of tubular reactor is 4~10mm, length is 20~
80m。
Compared with prior art, the invention has the following beneficial technical effects:
Preparation method of the invention carries out the preparation that polyacrylamide nano is microballoon by using tubular reactor, has
The features such as continuity of operation, easily-controlled reaction conditions, the reaction time is short, highly-safe, in addition the present invention passes through tubular reactor
The strong feature of internal microstructure features and heat and mass power carries out rapid polymerization reaction to acrylamide, and controllability is strong, gathers
The conversion ratio for closing reaction is greater than 99%, and particle diameter distribution width is narrow.The present invention can directly apply actual production, no enlarge-effect, and
It can be accomplished scale production according to needs of production.The detection of crude product postmenstruation shows: particle diameter distribution is 110~117nm, whole
Precursor reactant conversion ratio 99%.
Further, by using compressed air bubble techniques, the liquid flow containing acrylamide is in pipeline by bubble point
It is divided into discontinuous segment, polymerization reaction heat release is limited inside every section of liquid material, due to the biggish specific surface of tubular reactor
Product has more efficient heat transfer property, and heat of reaction is taken away rapidly, avoids reaction caused by heat aggregation and automatically speeds up now
As ensure that the steady and controllability of polymerization reaction.The rear volume expansion in addition, compressed air bubble is heated in pipeline, indirectly
Pushed travel rate of the material in pipeline, and when it is flowed in pipeline inner wall of the pipe attachment can be formed it is strong
Scouring effect avoids acrylamide monomer adherency tube wall and forms gel, it is clear to reduce equipment while improving product quality
Reason maintenance cycle.Finally, due to which the entrance of compressed air bubble causes manifold pressure to increase, it is suppressed that the life of foam when polymerization
At reaction more can be carried out steadily.
After improvement, feeding temperature be can be improved to 80 DEG C or more, and the reaction time shortened within 1 hour, to substantially reduce
Energy consumption, improves the economic benefit of production process, while reducing security risk.
Preparation facilities of the invention is introduced by the way that reaction raw materials are arranged in different reaction kettles, then by different raw materials
Tubular reactor carries out the preparation that polyacrylamide nano is microballoon, has continuity of operation, easily-controlled reaction conditions, when reaction
Between it is short, it is highly-safe the features such as, in addition the present invention is by microstructure features inside tubular reactor and heat and mass power strong
Feature carries out rapid polymerization reaction to acrylamide, and controllability is strong.The present invention can realize scale according to needs of production
Change, continuous production.Apparatus of the present invention are simple, and the polyacrylamide nano microspheres quality of preparation is stablized, and uniform particle diameter avoids
Excessive kettle and sudden and violent poly- phenomenon in traditional autoclave production technology, improve product quality and production efficiency.
Detailed description of the invention
Fig. 1 is the schematic device that tubular reactor synthesizes polyacrylamide nano microballoon；
Wherein, A is acrylamide aqueous solution and crosslinking agent mixing kettle, and B is surfactant mixing kettle, and C is compressed air
Machine, D are acrylamide raw material mixing kettle, and E is bubbler, and F is tubular reactor, and G is insulating box, and H is product collecting pit；
Fig. 2 is the grain size distribution of the embodiment of the present invention, wherein (a) is 1 grain size distribution of embodiment；It (b) is embodiment
2 grain size distributions；It (c) is 3 grain size distribution of embodiment；It (d) is 4 grain size distribution of embodiment；It (e) is 5 partial size of embodiment point
Butut；It (f) is 6 grain size distribution of embodiment；It (g) is 7 grain size distribution of embodiment；It (h) is 8 grain size distribution of embodiment.
Specific embodiment
Embodiments of the present invention are described in further detail below:
As shown in Figure 1, the present invention provides a kind of preparation facilities of polyacrylamide nano microballoon, including acryloyl aqueous amine
Solution and crosslinking agent mixing kettle A, surfactant mixing kettle B, air compressor C, acrylamide raw material mixing kettle D, bubbler
E, tubular reactor F, insulating box G and product collecting pit H；The acrylamide aqueous solution and crosslinking agent mixing kettle A, surface are living
Property agent mixing kettle B outlet end connection acrylamide raw material mixing kettle D input end, the outlet of acrylamide raw material mixing kettle D
The liquid feeding end of end connection tubular reactor F；The input end of the outlet end connection bubbler E of air compressor C, bubbler E's goes out
The inlet end of mouth end connection tubular reactor F, the discharge end of tubular reactor F are connected to product collecting pit H；Tubular reactor F
It is arranged in insulating box G；Acrylamide raw material mixing kettle D is provided with initiator feed opening.
The device further includes two micro- constant-flux pumps for being respectively used to conveying liquid material and compressed air, wherein for conveying
The outlet end of micro- constant-flux pump of liquid material is connected to tubular reactor F import, and micro- advection for conveying compressed air pumps out
Mouth end is connected to the leading portion of tubular reactor F.
The tubular reactor is single hose reactor, and the internal diameter of tubular reactor is 4~10mm, length is 20~
80m。
The present invention also provides a kind of preparation methods that polyacrylamide nano is slight, by acrylamide aqueous solution, crosslinking
Agent, surfactant are stirred mixing by mixing kettle, and initiator is added, then introduce in a continuous manner with compressed air
In tubular reactor, liquid material and compressed air enter the overall flow rate of tubular reactor for 50~600mL/min, so that propylene
Polymerization reaction occurs for amide, and reaction temperature is 55~85 DEG C, and the time is 500~1500s, is made micro- comprising polyacrylamide nano
Then the logistics of ball draws the logistics comprising polyacrylamide nano microballoon from tubular reactor, obtain poly- third through collecting
Acrylamide nanosphere finished product.
Wherein, initiator is the di-tert-butyl hydrogen peroxide that mass concentration is 98%；Initiator amount account for acrylamide and
The 0.1%~1.5% of crosslinking agent gross mass, crosslinking agent are the N that mass concentration is 99%, penylene bismaleimide between N-, pressure
Contracting air input volume is the 0.1%~1.5% of liquid material volume；The tubular reactor is respectively used to defeated including two
Micro- constant-flux pump of liquid material and compressed air is sent, the outlet end of three micro- constant-flux pumps is connected to micro-mixer, micro-mixer
Outlet end is connected to tubular reactor, and the outlet end of tubular reactor is connected with product collector.
Tubular reactor is tubular reactor, and the internal diameter of tubular reactor is 4~10mm, and length is 20~80m, feature
It is that inside is bigger than table heating surface area, heat transfer rate is fast, and it is anti-can to complete polymerization under limit reaction temperature with most fast conversion rate
It answers, significantly reduces the reaction time.Number can be realized using the technological parameter that tubular reactor prepares polyacrylamide nano microballoon
Amount amplification, produces, no enlarge-effect on demand；Insulating box is provided on the outside of tubular reactor.
Wherein, by using compressed air bubble techniques, the liquid flow containing acrylamide exists the intake method of compressed air
By bubble partition at discontinuous segment in pipeline, polymerization reaction heat release is limited inside every section of liquid material, due to pipe reaction
The biggish specific surface area of device has more efficient heat transfer property, and heat of reaction is taken away rapidly, caused by avoiding heat aggregation
Reaction automatically speeds up phenomenon, ensure that the steady and controllability of polymerization reaction.In addition, after compressed air bubble is heated in pipeline
Volume expansion has pushed travel rate of the material in pipeline indirectly, and when it is flowed in pipeline can be attached to inner wall of the pipe
Object form strong scouring effect, avoid acrylamide monomer adherency tube wall formed gel, improve the same of product quality
When reduce equipment cleaning maintenance cycle.Finally, due to which the entrance of compressed air bubble causes manifold pressure to increase, it is suppressed that
The generation of foam when polymerization, reaction more can be carried out steadily.
Preparation method of the invention is described in further detail with reference to the accompanying drawings and examples:
Embodiment 1
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 5 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 50mL/min of compressed air, acrylamide and crosslinking agent is 1:0.001, and initiator amount is acrylamide
With the 0.01% of crosslinking agent gross mass, compressed air input volume is the 0.1% of liquid material volume as far as possible.Tubular reactor F
Internal diameter is 4mm, and length 80m is placed in insulating box G, and reaction temperature is 55 DEG C, reaction time 1206s.Material exists
Enter in product collector H after sufficiently being reacted in tubular reactor.W-response conversion ratio is 90.73%.
Gained sample dispersion in embodiment 1 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 114nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 1
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.89MPa, permeability decrease 21.84md, breakthrough pressure 2.79MPa.
Embodiment 2
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 15 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 60mL/min of compressed air, acrylamide and crosslinking agent is 1:0.01, and initiator amount is acrylamide
With the 0.03% of crosslinking agent gross mass, compressed air input volume is the 0.3% of liquid material volume as far as possible.Tubular reactor F
Internal diameter is 6mm, and length 50m is placed in insulating box G, and reaction temperature is 60 DEG C, reaction time 1413s.Material exists
Enter in product collector H after sufficiently being reacted in tubular reactor.W-response conversion ratio is 93.42%.
Gained sample dispersion in embodiment 2 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 117nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 2
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.27MPa, permeability decrease 20.31md, breakthrough pressure 2.47MPa.
Embodiment 3
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 9 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 600mL/min of compressed air, acrylamide and crosslinking agent is 1:0.04, and initiator amount is acrylamide
With the 0.12% of crosslinking agent gross mass, compressed air input volume is the 0.5% of liquid material volume as far as possible.Tubular reactor F
Internal diameter is 10mm, and length 80m is placed in insulating box G, and reaction temperature is 62 DEG C, reaction time 628s.Material exists
Enter in product collector H after sufficiently being reacted in tubular reactor.W-response conversion ratio is 92.40%.
Gained sample dispersion in embodiment 3 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 111nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 3
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.22MPa, permeability decrease 20.37md, breakthrough pressure 2.50MPa.
Embodiment 4
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 20 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 400mL/min of compressed air, acrylamide and crosslinking agent is 1:0.13, and initiator amount is acrylamide
With the 0.22% of crosslinking agent gross mass, compressed air input volume is the 0.25% of liquid material volume as far as possible.Tubular reactor F
Internal diameter is 8mm, and length 70m is placed in insulating box G, and reaction temperature is 68 DEG C, reaction time 527s.Material exists
Enter in product collector H after sufficiently being reacted in tubular reactor.W-response conversion ratio is 93.68%.
Gained sample dispersion in embodiment 4 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 113nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 4
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.40MPa, permeability decrease 21.00md, breakthrough pressure 2.43MPa.
Embodiment 5
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 26 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 80mL/min of compressed air, acrylamide and crosslinking agent be 1:0.2, initiator amount be acrylamide with
The 0.35% of crosslinking agent gross mass, compressed air input volume are the 0.5% of liquid material volume as far as possible.In tubular reactor F
Diameter is 8mm, and length 20m is placed in insulating box G, and reaction temperature is 73 DEG C, reaction time 754s.Material is in pipe
Enter in product collector H after sufficiently being reacted in formula reactor.W-response conversion ratio is 96.62%
Gained sample dispersion in embodiment 5 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 110nm.(See Figure 2) specially marks the standard that committee promulgates according to petroleum
Related technical indicator is surveyed in " measurement of 5345 oil-water relative permeability of SY/T " and " 6379 performance of profile modification evaluation method of SY/T "
Fixed and requirement, accurately weighs the polyacrylamide nano microsphere sample 0.5g in embodiment 5, is added to simulation oil field water flooding
It is fully dispersed in 99.5g, for use.Under 60 DEG C of constant temperatures, it is real that simulation oil field water flooding is injected into reservoir core plugging agent evaluation
In experiment device, data are recorded, then configured nanosphere dilution is injected into reservoir core plugging agent evaluation experimental device, remembered
Record data simultaneously compare, and improve 6.72MPa, permeability decrease using injection pressure after nanosphere as the result is shown
20.11md, breakthrough pressure 2.38MPa.
Embodiment 6
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 40 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 70mL/min of compressed air, acrylamide and crosslinking agent is 1:0.18, and initiator amount is acrylamide
With the 0.4% of crosslinking agent gross mass, compressed air input volume is the 0.8% of liquid material volume as far as possible.In tubular reactor F
Diameter is 5mm, and length 60m is placed in insulating box G, and reaction temperature is 80 DEG C, reaction time 1010s.Material is in pipe
Enter in product collector H after sufficiently being reacted in formula reactor.W-response conversion ratio is 96.13%.
Gained sample dispersion in embodiment 6 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 111nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 6
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.45MPa, permeability decrease 20.23md, breakthrough pressure 2.53MPa.
Embodiment 7
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 36 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 200mL/min of compressed air, acrylamide and crosslinking agent is 1:0.16, and initiator amount is acrylamide
With the 0.30% of crosslinking agent gross mass, compressed air input volume is the 1.3% of liquid material volume as far as possible.Tubular reactor F
Internal diameter is 8mm, and length 70m is placed in insulating box G, and reaction temperature is 85 DEG C, reaction time 1055s.Material exists
Enter in product collector H after sufficiently being reacted in tubular reactor.W-response conversion ratio is 99.32%.
Gained sample dispersion in embodiment 7 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 112nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 7
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.52MPa, permeability decrease 21.02md, breakthrough pressure 2.87MPa.
Embodiment 8
As shown in Figure 1, acrylamide aqueous solution, crosslinking agent, surfactant are transferred to from A, B by mechanical pump respectively
In mixing kettle, initiator is added, it is agitated to be delivered in tubular reactor by feed pump after mixing, while opening sky
Compressed air is pumped into micro-pipe by bubbler with 28 beats/min of frequency and reacts leading portion entrance by air compressor.Liquid material with
The molar ratio of the total rate 70mL/min of compressed air, acrylamide and crosslinking agent be 1:0.2, initiator amount be acrylamide with
The 0.40% of crosslinking agent gross mass, compressed air input volume are the 1.5% of liquid material volume as far as possible.In tubular reactor F
Diameter is 8mm, and length 20m is placed in insulating box G, and reaction temperature is 82 DEG C, reaction time 862s.Material is in pipe
Enter in product collector H after sufficiently being reacted in formula reactor.W-response conversion ratio is 98.97%.
Gained sample dispersion in embodiment 8 is stirred 1 hour in 3# white oil, after ultrasonic wave disperses 10min, passes through horse
Your initial size of literary laser diffraction analyzer measurement microballoon is 111nm.(See Figure 2)
The standard " measurement of 5345 oil-water relative permeability of SY/T " and " SY/T6379 profile control that committee promulgates specially are marked according to petroleum
Agent method of evaluating performance " in the measurement of related technical indicator and require, accurately weigh the polyacrylamide nano microballoon in embodiment 8
Sample 0.5g is added in simulation oil field water flooding 99.5g, fully dispersed, for use.Under 60 DEG C of constant temperatures, by simulation oil
Field water flooding is injected into reservoir core plugging agent evaluation experimental device, records data, then configured nanosphere dilution is infused
Enter into reservoir core plugging agent evaluation experimental device, record data and compare, as the result is shown using injection pressure after nanosphere
Power improves 6.93MPa, permeability decrease 20.02md, breakthrough pressure 2.48MPa.
It is basic to can be seen that the polyacrylamide nano microspherulite diameter prepared using the technique from testing result chart data
Between 110~120nm, particle size distribution range is narrow for control.Simultaneously using reservoir core plugging evaluation method to sample in embodiment into
Row performance test, all samples show certain closure function, after use, due to the infiltration drops of water, earth's surface
Pressure is restored again, can meet oil field deep water-drive oil recovery requirement.Simultaneously because each sample partial size degree is uniform, therefore experimental data
Between it is substantially parallel, also show microballoon stay in grade, no significant difference.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of polyacrylamide nano microballoon, which is characterized in that by acrylamide, crosslinking agent, surface-active
The liquid material and compressed air of agent and initiator composition are introduced into tubular reactor in a continuous manner, so that decomposition of initiator
It generates free radicals, causes the polymerization reaction of acrylamide, the logistics comprising polyacrylamide microsphere is made, then will include poly- third
The logistics of acrylamide is drawn from tubular reactor, obtains polyacrylamide nano finished microballoon products through collecting；
Wherein, the molar ratio of acrylamide and crosslinking agent is 1:(0.001~0.2), initiator amount accounts for acrylamide and crosslinking
The 0.01%~0.4% of agent gross mass.
2. a kind of preparation method of polyacrylamide nano microballoon according to claim 1, which is characterized in that compressed air
Tubular reactor is passed through by way of bubbling, the liquid flow containing acrylamide is in pipeline by bubble partition at discontinuous segment.
3. a kind of preparation method of polyacrylamide nano microballoon according to claim 1 or 2, which is characterized in that compression
Air input volume is the 0.1%~1.5% of liquid material input volume, and it is 5~40 beats/min that compressed air, which is pumped into frequency,.
4. a kind of preparation method of polyacrylamide nano microballoon according to claim 1, which is characterized in that the pipe
The outside of formula reactor is provided with insulating box；The temperature of insulating box is 50~90 DEG C.
5. a kind of preparation method of polyacrylamide nano microballoon according to claim 1, which is characterized in that liquid material
And it is 50~600mL/min that compressed air, which enters the overall flow rate of tubular reactor,.
6. a kind of preparation method of polyacrylamide nano microballoon according to claim 1, which is characterized in that the friendship
Connection agent is N, penylene bismaleimide between N-；The initiator is di-tert-butyl hydrogen peroxide.
7. a kind of preparation method of polyacrylamide nano microballoon according to claim 1, which is characterized in that polymerization reaction
Temperature be 55~85 DEG C, the time be 500~1500s.
8. a kind of preparation facilities of polyacrylamide nano microballoon, which is characterized in that including acrylamide aqueous solution and crosslinking agent
Mixing kettle (A), surfactant mixing kettle (B), air compressor (C), acrylamide raw material mixing kettle (D), bubbler (E),
Tubular reactor (F), insulating box (G) and product collecting pit (H)；The acrylamide aqueous solution and crosslinking agent mixing kettle (A),
The input end of outlet end connection acrylamide raw material mixing kettle (D) of surfactant mixing kettle (B), the mixing of acrylamide raw material
The liquid feeding end of outlet end connection tubular reactor (F) of kettle (D)；Air compressor (C) outlet end connection bubbler (E) into
Mouth end, the inlet end of outlet end connection tubular reactor (F) of bubbler (E), the discharge end of tubular reactor (F) are connected to production
Product collecting pit (H)；Tubular reactor (F) setting is in insulating box (G)；The acrylamide raw material mixing kettle (D)
It is provided with initiator feed opening.
9. a kind of preparation method of polyacrylamide nano microballoon according to claim 8, which is characterized in that further include two
A micro- constant-flux pump for being respectively used to conveying liquid material and compressed air, wherein being used to convey going out for micro- constant-flux pump of liquid material
Mouth end is connected to tubular reactor (F) import, and micro- constant-flux pump outlet end for conveying compressed air is connected to tubular reactor
(F) leading portion.
10. a kind of preparation method of polyacrylamide nano microballoon according to claim 8, which is characterized in that described
Tubular reactor is single hose reactor, and the internal diameter of tubular reactor is 4~10mm, and length is 20~80m.
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