CN107163156B - Glucomannan based on nanotechnology preparation and its application in the oil industry - Google Patents
Glucomannan based on nanotechnology preparation and its application in the oil industry Download PDFInfo
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- CN107163156B CN107163156B CN201710346363.4A CN201710346363A CN107163156B CN 107163156 B CN107163156 B CN 107163156B CN 201710346363 A CN201710346363 A CN 201710346363A CN 107163156 B CN107163156 B CN 107163156B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/009—Konjac gum or konjac mannan, i.e. beta-D-glucose and beta-D-mannose units linked by 1,4 bonds, e.g. from Amorphophallus species; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- C—CHEMISTRY; METALLURGY
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
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- C—CHEMISTRY; METALLURGY
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/24—Bacteria or enzyme containing gel breakers
Abstract
A nanometer method for Portugal's mannose is produced the invention discloses a kind of, include multiple steps, so that raw material is crushing and processing 15-90 minutes in pulverization cylinder, the velocity of rotation for controlling stirring rod simultaneously is 500-4000 revs/min, and the control of the frequency of ultrasonic wave is finally refined 10-70 minutes in airslide disintegrating mill in the range of 20k-50kHz；It is the nanometer Glucomannan in 200-400nm that final production, which goes out partial size, and the molecular weight distribution of the Glucomannan is controlled in 100,000-20 ten thousand Da.Diverting agent is formed by biological enzyme formulation is added in these nanometer of Glucomannan, viscosity properties are significantly improved, and have more outstanding performance.The present invention is mutually bridged using these macromolecular substances, and thin and tough and tensile diaphragm is formed on the borehole wall, and adhesiveness is strong, can block crack, and bearing strain ability is strong, has preferable elongation, while being easy to carry out brokenly glue to return row.
Description
Technical field
The present invention relates to a kind of nanometer of refinement technology, further relate to using the Glucomannan of technology preparation and its in petroleum work
Application in industry.
Background technique
Nanometer (English: nanometre) is length unit, and International System of Units symbol is nm.Original claims millimicron, is exactly 10-9
Rice (1/1000000000th meter), i.e., 10-6Millimeter (1/1000000th millimeters).As centimetre, decimeter with meter as, be length
Linear module.4 times of atom sizes are equivalent to, the length than single bacterium is also small.International common name is nanometer, letter
Write nm.
The preparation method of nanoparticle is generally divided into two major classes at present: physical method and chemical method.Physical method is also known as
For comminuting method, it be by solid material from large to small, i.e., cake mass is crushed and nano-powder particle is made；Chemical method is also known as
Method for constructing, it is by lower limit atom, ion, molecule by being nucleated and growing two stage nano materials.Using chemistry as base
Available several nanometers of the powder of the nano-powder manufacturing method of plinth.But manufacturing cost is sometimes quite high, and is not easy to amplify, partial size
Distribution is also relatively uneven.Pulverize the mistake for referring to and object grain particle being crushed to small particle using mechanical or hydrokinetic approach
Journey.
Mode according to cohesive force between destruction material molecule is different, and current Ultra-Micro Grinding Equipment can be divided into mechanical crushing
Machine, airslide disintegrating mill, ultrasonic grinder etc..
Currently, nanometer pulverization equipment mainly have multi-D swing high energy nanon ball-mill, multilayer classifying nano ball grinding machine,
High speed nano grinder, high speed shear ultrafine crusher, airslide disintegrating mill, ultrasonic wave nano grinder etc..
The main component of fine powder is Glucomannan after konjaku processing, and also known as konjaku glucomannan (KGM), Glucomannan are
Know the maximum natural macromolecule amylose of viscosity in natural plant gum, is polymerize by glucose and mannose and form heteroglycan.Average molecular weight
It is 200,000-200 ten thousand, it is the glucose and mannose for being 1:1.6 by molecular proportion that shape is white or cream is to light brown yellow powder
Residue is polymerized by β-(Isosorbide-5-Nitrae)-glycosidic bond, and there are the branches of β (1,3) glycosidic bond composition on certain saccharide residue C-3, main
Every 32-80 saccharide residue has 1 branch on chain, and every branch has several to tens saccharide residues, every about 19 sugar on main chain
There is the acetyl group combined with ester bond on residue.It is 1.12 × 10 using the KGM weight average molecular weight that light scattering method measures6Or
2.619×105, and the viscosity average molecular weigh for measuring KGM is 8.09 × l05.KGM solid has the fibrous strands pattern of regularity, KGM
Between there are a large amount of hydrogen bonds, and not formed stable crystallization, but exist with amorphous state；KGM in presence of water, will divide
A large amount of hydrogen bond is formed between subchain to maintain the state of micelle in solution, and the size of micelle is in nanoscale.
Konjaku glucomannan has a variety of excellent characteristics, such as gelation, edibility, film forming, therefore in food, doctor
Each production field such as medicine, chemical industry has extensive purposes.But konjaku Portugal Glucomannan has the spies such as the low, poor fluidity of solubility
Property, application be subject to certain restrictions, for the performance for further increasing KGM, expand its application range, usually by physical method,
The means such as chemical method and bioanalysis degrade to it.
The fracture of high molecular polymer can be generally divided on microcosmic it is intermolecular slip, Van der Waals force or hydrogen bond destroy and
Chemical bond destroys three types.The destruction of first two type not will cause the degradation of molecule, and the destruction of only chemical bond just may be used
It can cause the degradation of molecule.Polymer plasticates in polymerization, melting extrusion and Polymer Solution is stirred strongly or ultrasonic wave is made
Used time may all make macromolecular chain be broken and degrade.The mechanical force and chemical signs of degradation of konjaku glucomannan is for actual production
With important inspiration meaning.
Particle is small solid, liquid or gas under the cutting state, be also possible to have vital microorganism,
Bacterium, virus etc..In most cases, one word of particle refers to solid particle, and liquid particles and gas particles then correspondingly become
Drop and bubble.Particle system is become by the particle swarm that many a particles form.Powder is then solid particle under rarefaction
Accumulation.What particle swarm or particle system were made of many particles.If all particles of composition particle swarm all have identical or close
Like identical granularity, then the particle swarm is referred to as monodispersed.When particle swarm is made of particle not of uniform size, then become more points
Scattered.
Current nanometer pulverization technology is varied, but the nano-scale particle after crushing is unable to accurately control its molecule
Amount, needs to crush and then measure screening, to obtain the product of needs.A large amount of work has just been lost in this.
Konjaku glucomannan, wherein glucose, mannose ratio are 1:1.6~1.7, and main chain is connected with β-Isosorbide-5-Nitrae-glycosidic bond
It connects, branch is with 1-3 glucosides key connection, and molecular weight is up to 1,000,000 grades.Hydrosol large viscosity has typical pseudoplastic behavior.Its is good
The performances such as good thickening, blending, sizing, gelling, film forming, lubrication and bio-compatible have been widely used for petroleum industry, food,
The fields such as packaging, coating, biological medicine and makeup.Especially in petroleum industry using increasingly extensive.
Application in the oil industry includes the application of drilling fluid and the utilization in DP technology.It can be in diverting agent, leak stopping
It is applied in agent, tackifier, fracturing fluid, Weak Gels and corrosion inhibiter.
Konjaku polymer temporarily blocked drilling fluid mainly utilize konjaku glucomannan macromolecular link network on well (hole) wall every
Film effect.These macromolecular substances mutually bridge, and are attached on well (hole) wall after filter is remaining and form diaphragm, these diaphragms are thin and tough and tensile,
Permeability is extremely low, it is sufficient to meet temporarily stifled require.Konjaku polymer bores simultaneously and liquid has good encapsulating ability, can be effectively
Inhibit the dispersion of drilling cuttings.
The preparation of special compositional biological enzyme will be matched, has been added in the solution of konjaku polymer.Biological enzyme formulation conduct
Biocatalyst can control the degradation speed that polymer is become short chain small molecule by long-chain macromolecule.Terminate in drilling work
Afterwards, polymer molecule becomes short chain by long-chain, and the viscosity of drilling fluid is reduced taking human as controllable mode.With drilling fluid viscosity
It reduces, the mudcake being previously formed is abolished automatically, and the mobility enhancing of production formations fluid reaches to restore the permeability on simultaneously all stratum
To the purpose for improving oil gas well production.
It is compared with traditional temporary plugging technique, the advantages of konjaku temporarily blocked drilling fluid is presented as automatic degradation, fundamentally changes
Into de-plugging process, production efficiency is improved, and de-plugging cost is greatly saved.Biological enzyme can effective and degradable polymerization
Object, therefore konjaku temporarily blocked drilling fluid avoids drilling and completes post-consumer polymer to the injury problem of payzone.
But the konjaku glucomannan molecular weight that current konjaku temporarily blocked drilling fluid uses is excessive, is million grades, this makes
Its performance not enough meets modern drilling well and requires.
Sichuan, North China Oilfield research and konjaku fracturing fluid is applied, consisting of: 0.5% modified konjaku glue+0.15%
+ 0.012% potassium peroxydisulfate of organic titanium or borax.Its main performance is as follows:
1. rheological characteristic: 90 degrees Celsius, 170s-1Lh or so is sheared, is measured with RV20 rotational viscometer, K=4026Pa
S0.35:
2. temperature resistance shear resistant: 90 degrees Celsius, 170s-1Shear 60min (wherein heating shearing 20min, 90 degrees Celsius of perseverances
Warm 40min), viscosity 78.8mPaS；
3. temperature stability: 90 degrees Celsius of constant temperature 60min, in 170s-1Under viscosity be 235.9mPaS；
4. leak-off: 70 degrees Celsius, 3.5MPa, two filter paper measurements, leakoff coefficent is 8.56 × 10-4m/min1/2
Summary of the invention
The present invention aiming at the shortcomings in the prior art, provides a kind of nanometer preparation method of Glucomannan, can pass through
The partial size of product obtains molecular weight distribution collection to accurately control the molecular weight of product after dispersion and fining after control refinement
In nano functional sugar, the technical method is more convenient, environmentally friendly, and cost reduces, more commercial competitiveness；These macromolecular Portugals are sweet poly-
Sugared mutually bridge joint, forms thin and tough and tensile diaphragm on the borehole wall, and adhesiveness is strong, can block crack, and bearing strain ability is strong, tool
There is preferable elongation, while being easy to carry out brokenly glue to return row, is highly suitable in petroleum industry using as diverting agent.
In order to solve the above-mentioned technical problem, the present invention is addressed by following technical proposals: a kind of production nanometer Portugal is sweet
The method of glycan, including step 1, by Glucomannan material crushing and processing 15-90 minutes in pulverization cylinder, the rotation of stirring rod
Speed is 500-4000 revs/min；Step 2 starts discharge belt, and the material that paddle rotation is brought up is delivered to and is gathered materials
In bucket；Step 3, the material in aggregate bin is delivered to airslide disintegrating mill by the first discharge nozzle by starting pump, and passes through second
Discharge nozzle is delivered to the first high-pressure pump；Step 4 starts the first high-pressure pump, and material is sprayed into air-flow crushing by the first air jet pipe
It collides in machine and from the material that the first discharge nozzle exports, then stops the first high-pressure pump；Step 5 starts the second high-pressure pump,
Material is sprayed into airslide disintegrating mill by the second air jet pipe and internal material collides, then stops the second high-pressure pump；Step
Rapid six, start third high-pressure pump, material is sprayed into airslide disintegrating mill by third air jet pipe and internal material collides, so
Stop third high-pressure pump afterwards；Step 7, repeats step 3 to six, repetition time 10-70 minute, while starting ultrasonic wave
Device, the frequency of ultrasonic wave are 20k-50kHz；Step 8, material transfer portion by the material transportation collected from discharge nozzle to finished bin,
Material in finished bin is a nanometer Glucomannan.
A kind of nanometer Glucomannan produced with the aforedescribed process, the partial size of the nanometer Glucomannan are 200-
400nm, molecular weight distribution are 100,000-20 ten thousand Da.It is poly- that mannosan in this partial size and molecular weight ranges is referred to as sweet dew Asia
Sugar or nanometer sweet dew Asia glycan.
A kind of nanometer Glucomannan of above-mentioned method production is added in nanometer Glucomannan in the application of petroleum industry
Biological enzyme formulation forms diverting agent, and viscosity properties are improved, temperature resistance shear resistant: 90 degrees Celsius, 170s-1Shear 60min (its
20min, 90 degrees Celsius of constant temperature 40min are sheared in middle heating), viscosity 2300-3100mPaS；Temperature stability: 90 degrees Celsius
Constant temperature 60min, in 170s-1Under viscosity be 1800-2100mPaS.
Glucomannan is crushed to nanoscale particle using nanometer pulverization device by the present invention, controls the partial size of these particles
In the range of 200-400nm, to obtain polyoses grain of the molecular weight distribution in 100,000-20 ten thousand Da, these macromoleculars
Substance mutually bridges, and thin and tough and tensile diaphragm is formed on the borehole wall, and adhesiveness is strong, can block crack, and bearing strain ability is strong,
With preferable elongation, while being easy to carry out brokenly glue to return row.
Detailed description of the invention
Fig. 1 is pulverization cylinder structural schematic diagram of the present invention.
Fig. 2 is airslide disintegrating mill structural schematic diagram of the present invention.
Fig. 3 is the Pneumatic crushing machine gaseous flow diagram of the present invention.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing: as shown in Figure 1 to Figure 3, one
The method that kind produces nanometer Glucomannan, including step 1, by Glucomannan material crushing and processing 15-90 points in pulverization cylinder 1
Clock, the velocity of rotation of stirring rod 13 are 500-4000 revs/min；Step 2 starts discharge belt 15, paddle 131 is rotated
The material brought up is delivered in aggregate bin 31；Material in aggregate bin 31 is passed through the first discharge nozzle by step 3, starting pump 3
321 are delivered to airslide disintegrating mill 4, and are delivered to the first high-pressure pump by the second discharge nozzle 322；Step 4, starting first are high
Material is sprayed into airslide disintegrating mill 4 by the first air jet pipe 5 and is collided from the material that the first discharge nozzle 321 exports by press pump
It hits, then stops the first high-pressure pump；Step 5 starts the second high-pressure pump, and material is sprayed into air-flow crushing by the second air jet pipe 6
It collides in machine 4 with internal material, then stops the second high-pressure pump；Step 6 starts third high-pressure pump, and material is passed through the
Three air jet pipes 42 spray into airslide disintegrating mill 4 and internal material collides, and then stop third high-pressure pump；Step 7 repeats
Step 3 is to six, repetition time 10-70 minute, while starting supersonic generator 7, and the frequency of ultrasonic wave is 20k-50kHz；Step
Rapid eight, by from the material transportation that discharge nozzle 41 is collected to finished bin, the material in finished bin is that nanometer Portugal is sweet poly- in material transfer portion
Sugar.
The method of above-mentioned preparation nanometer Glucomannan, needs using nanometer preparation facilities, which includes pulverization cylinder 1,
It is provided with stirring rod 13 in the pulverization cylinder 1, the paddle 131 of upper and lower spiral, the crushing are provided in the stirring rod 13
1 bottom of cylinder is provided with motor 11, and the output shaft 12 of the motor 11 is connected with the stirring rod 13, and 1 bottom of pulverization cylinder is set
It is equipped with feed pipe 14, discharge belt 15 is provided at the top of the pulverization cylinder 1, the discharge belt 15 is close to the stirring
The top of leaf 131, is provided with cooling cylinder 2 outside the pulverization cylinder 1, and 2 bottom of cooling cylinder is provided with water inlet pipe 21 and top
Outlet pipe 22 is connected on side wall, the other end of the discharge belt 15 is set to 31 top of aggregate bin, the aggregate bin 31
Lower section is connected with pump 3, and the pump 3 is provided with discharging portion 32, and the discharging portion 32 is provided with the first discharge nozzle 321 and the second discharging
Pipe 322, first discharge nozzle 321 are connected with airslide disintegrating mill 4, and 4 side wall of airslide disintegrating mill is provided with the first air jet pipe 5
With the second air jet pipe 6, third air jet pipe 42, first air jet pipe 5, the second jet are provided at the top of the airslide disintegrating mill 4
The central axes of pipe 6 and third air jet pipe 42 intersect at a point, and second discharge nozzle 322 is connected with the first high-pressure pump and second high
Press pump, the output end of first high-pressure pump connect first air jet pipe 5, described in the output end connection of second high-pressure pump
Second air jet pipe 6, the third air jet pipe 42 are connected with third high-pressure pump, and 4 bottom of airslide disintegrating mill is provided with discharge nozzle
41, the discharge nozzle 41 is connected with material transfer portion, the material transfer portion connect first high-pressure pump, the second high-pressure pump and
Third high-pressure pump, the material transfer portion are also connected with finished bin, and baffle portion 45 is set in the airslide disintegrating mill 4, described
Drainage inclined-plane 44 is provided in baffle portion 45, the drainage inclined-plane 44 and the airslide disintegrating mill are provided with arc between 4 top
Drainage cambered surface 43,43 end of drainage cambered surface is connected with the third air jet pipe 42, is provided with grinding in the pulverization cylinder 1
Ball, annular is provided with two circle ultrasonic wave portions on 4 outer wall of airslide disintegrating mill, and every circle ultrasonic wave portion is provided with odd number ultrasonic wave
Generator 7.
When being refined, because this programme can generate more heat using physics mode.In powder
It is provided with cooling cylinder 2 outside broken cylinder 1, temperature control is carried out by way of water cooling.Temperature control portion 8 is provided with outside airslide disintegrating mill 4.Control
There is interval on 4 outer wall of warm portion 8 and airslide disintegrating mill, water can be injected in this interval and carries out temperature control, injection can also be passed through
The lower gas of temperature carries out cooling temperature control.
A kind of nanometer Glucomannan produced with the aforedescribed process, the partial size of the nanometer Glucomannan are 200-
400nm, molecular weight distribution are 100,000-20 ten thousand Da.It is poly- that mannosan in this partial size and molecular weight ranges is referred to as sweet dew Asia
Sugar or nanometer sweet dew Asia glycan.
A kind of nanometer Glucomannan of above-mentioned method production is added in nanometer Glucomannan in the application of petroleum industry
Biological enzyme formulation forms diverting agent, and viscosity properties are improved.Average value is measured into after crossing many experiments detection, knows following number
According to: temperature resistance shear resistant: 90 degrees Celsius, 170s-160min (wherein heating shearing 20min, 90 degrees Celsius of constant temperature 40min) is sheared,
Viscosity is 3012.7mPaS；Temperature stability: 90 degrees Celsius of constant temperature 60min, in 170s-1Under viscosity be 2135.7mPa
S。
The product cut size that nanometer refinement technology through the invention obtains, whole particle diameter distribution approximate normal distribution, absolutely
Most of partial size concentrates on 200-400nm, then by detection, the product that can determine is that molecular weight distribution is 100,000-20
In the range of ten thousand Da.Mechanical force forces the meta system of KGM by uniform sequential cutting, makes original macromolecular chain and hydrogen bond
Fracture obtains the lower oligosaccharide of molecular weight.
Nanometer refinement technology of the invention is the method for mixing refinement, by controlling the dispersion and fining time of machine, revolving speed
To control the partial size of finished product after dispersion and fining.
Because under the prior art detect polysaccharide molecular weight be a sufficiently complex cumbersome process, especially by chemistry or
The Glucomannan that person's biological mode is degraded, it is even more a cumbersome operation that molecular weight detection is carried out to it, and cost is very
It is high.The partial size overall distribution of the Glucomannan product of the nanometer device for thinning production provided in this programme is similar to normal distribution.
It is compared into excessively multiple detection, it is found that the partial size of the Glucomannan of present apparatus production is within the scope of 200-400nm, and phase
Corresponding molecular weight distribution is between 100,000-20 ten thousand Da.The Glucomannan of present apparatus production, partial size and molecular weight are presented
A kind of corresponding relationship.This just enormously simplifies detection process, as long as the partial size of detection particle, to save a large amount of work
Make the time.That is, the Glucomannan produced by the present apparatus, as long as by size controlling in the range of 200-400nm, energy
Enough guarantee molecular weight distribution between 100,000-20 ten thousand Da.
The present invention utilizes nanometer device for thinning that Glucomannan dispersion and fining to nanoscale particle, is controlled these particles
Partial size is in the range of 200-400nm, to obtain polyoses grain of the molecular weight distribution in 100,000-20 ten thousand Da, these are big
Molecular substance mutually bridges, and thin and tough and tensile diaphragm is formed on the borehole wall, and adhesiveness is strong, can block crack, bearing strain energy
Power is strong, has preferable elongation, while being easy to carry out brokenly glue to return row.
Main performance is as follows:
Temperature resistance shear resistant: 90 degrees Celsius, 170s-1Shear 60min (wherein heating shearing 20min, 90 degrees Celsius of constant temperature
40min), viscosity 2300-3100mPaS；
Temperature stability: 90 degrees Celsius of constant temperature 60min, in 170s-1Under viscosity be 1800-2100mPaS.
Compared with common million grades of Glucomannan particle, 100,000 grade particles generated by this method have more
Outstanding performance.Also, this method utilizes the size of grain diameter, so that it is determined that the distribution of molecular weight, so that result is more
Add precisely, and detection also becomes more convenient.Measurement partial size can use physical method, and if detection molecules amount, it needs
To use chemical mode.
The nanometer Glucomannan of this programme production, it can also be used to manufacture fracturing fluid.Fracturing fluid be during oil-gas mining,
In order to improve liquid used in fracture condudtiviy, its main function is shelly ground, causes the crack of certain geometric dimension,
It carries proppant and enters crack to predetermined position.With the appearance of the massive hydraulic fractures technologies such as horizontal well, batch production pressure break, to pressure
The prop-carrying capacity for splitting liquid proposes new requirement, and common way is to improve thickening agent dosage, reaches higher base fluid viscosity and frozen glue
Intensity is to realize that high sand ratio takes sand.But then, go deep into Reservoir Development, middle and low permeable reservoir is increasing,
The low residue of fracturing fluid, Low Damage are asked, the fracturing fluid of high thickening agent dosage is difficult to reach requirement.
The performance requirement of fracturing fluid: viscosity is high, and lubricity is good, and filter loss is small, low frictional resistance, to by the fluid layer of pressure break without stifled
Plug and damage, it is pollution-free to fluid mine, thermal stability and shearing stability property is good, low residue, good, the broken glue of compatibility rapidly, goods
Source is wide, convenient for preparing, economical rationality.
In existing oil/gas well hydraulic fracturing technology, using natural plant gum and their relevant chemically modified derivatives as pressure
The thickener of liquid is split in occupation of leading position.This kind of natural plant gum mainly has: guar gum, fenugreek gum, sesbania gum, cellulose, konjaku
Derivative after glue and chemical modification.In fracturing fluid other than above-mentioned natural plant gum thickener, it is necessary to be added in fracturing fluid
Relevant additive, to improve the comprehensive performance of fracturing fluid, to reduce injury of the fracturing fluid to oil-gas Layer.Simultaneously because fracturing fluid
In must use gel breaker, gel breaker reduce the viscosity of fracturing fluid always in fracturing process, affect the reliability of construction.And
And fracturing fluid must return after the completion of pressing crack construction and drain into ground, to the processing for draining into ground liquids is returned, have both at home and abroad stringent
Requirement, the liquid for the row of returning is not reusable, if be not effectively treated to it, easily pollutes the environment.
Konjaku glucomannan and other ingredients can carry out physical modification using the method for crushing and selection by winnowing.Carrying out crushing can
Konjaku glucomannan particle is set to become smaller coenobium, to be easier to water-soluble.In addition ingredient not soluble in water can be crushed
At smaller particle with benefit and konjaku glucomannan grain sorting.Modified, its heat-resisting property improves especially after physical modification
Larger, this is conducive to deep well drilling.
The method that konjaku glucomannan uses chemical modification to combine with physical modification, can be improved the water solubility of konjac glucomannan
And retaining wall performance, its broken glue residue is reduced, the few konjac glucomannan of high, the broken glue residue of good water solubility, water-soluble adhesiveness is obtained, it is right
Oil reservoir matrix and fracture conductivity damage are low, are conducive to the permeability for protecting oil reservoir gas, improve effect of increasing production.This modified evil spirit
Taro is pollution-free to stratum.
The nanometer Glucomannan of this programme manufacture, is used for manufacturing a kind of fracturing fluid of superior performance.It carries out by weight
It calculates, the raw material composition of fracturing fluid includes: 0.2-0.8 parts of nanometer Glucomannan, 0.3-0.7 parts of crosslinking agent, composite synergist
0.6-2.5 parts, 0.1-0.3 parts of water-soluble fibre, 0.1-3.5 parts of gel breaker and 100 parts of water.
Wherein, crosslinking agent include one of organic borate cross-linker, organic zirconium crosslinker and organic boron zirconium cross linking agent etc. or
Several combinations.If crosslinking agent include it is two or more in the substance, they can be mixed with arbitrary proportion, will not influence most
The performance of whole fracturing fluid.
Wherein, gel breaker includes the combination of one or more of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate etc..If broken
Jelly include it is two or more in the substance, they can be mixed with arbitrary proportion, will not influence the performance of final fracturing fluid.
Wherein, water-soluble fibre include polypropylene fibre, polyethylene fibre, polyacrylonitrile fibre, vinal and
The combination of one or more of polyester fiber etc..If water-soluble fibre include it is two or more in the substance, they can
It is mixed with arbitrary proportion, will not influence the performance of final fracturing fluid.Water-soluble fibre can reach in fracturing fluid of the invention
Improve the effect of fracturing fluid prop-carrying capacity.
Wherein, on the basis of the total weight of composite synergist, the raw material composition of the composite synergist includes: cationic surface
Activating agent 10-20%, nonionic surfactant 5-10%, long chain alkylammonium salts 10-30%, villaumite 20-40%, low molecule
The alcohol 20-40% and water surplus of amount.
Wherein, cationic surfactant includes cetylpyridinium chloride and/or chlorination octadecylpyridinium etc..If positive
Ionic surface active agent includes two kinds in the substance, then they can be mixed with arbitrary proportion, will not influence final fracturing fluid
Performance.
The nanometer Glucomannan of this programme manufacture, is used for manufacture fracturing fluid, this fracturing fluid can satisfy well temperature 170 and take the photograph
Fracture in oil and water wells construction requirement within family name's degree.Due in 80 degrees Celsius of pressing crack constructions of well temperature KGM fracturing fluid can use it is low
Warm crosslinking agent replaces high-temperature cross-linking agent, and cost is lower than guanidine gum fracturing fluid, will greatly save cost in this way.
By a large amount of indoor test and site operation experiment, KGM is in petroleum industry every field using very extensive.
Konjac glucomannan and guanidine glue, sesbania technical performance compared with, be better than them, and price is also more relatively cheap than them.Thus may be used
See that prospect of the KGM in petroleum industry field is considerable.Although the utilization of KGM in the oil industry is more and more extensive.
Protection scope of the present invention includes but is not limited to embodiment of above, and protection scope of the present invention is with claims
Subject to, replacement, deformation, the improvement that those skilled in the art that any pair of this technology is made is readily apparent that each fall within of the invention
Protection scope.
Claims (1)
1. a kind of method for producing nanometer Glucomannan, it is characterised in that: including step 1, by Glucomannan material in pulverization cylinder
(1) interior crushing and processing 15-90 minutes, the velocity of rotation of stirring rod (13) was 500-4000 revs/min；Step 2, starting discharging pass
Band (15) is sent, the material that paddle (131) rotation is brought up is delivered in aggregate bin (31)；Step 3, starting pump (3) will collect
Material in hopper (31) is delivered to airslide disintegrating mill (4) by the first discharge nozzle (321), and passes through the second discharge nozzle
(322) it is delivered to the first high-pressure pump；Step 4 starts the first high-pressure pump, and material is sprayed into air-flow powder by the first air jet pipe (5)
It collides in broken machine (4) and from the material that the first discharge nozzle (321) export, then stops the first high-pressure pump；Step 5, starting the
Material is sprayed into airslide disintegrating mill (4) by the second air jet pipe (6) and internal material collides, then stopped by two high-pressure pumps
Only the second high-pressure pump；Step 6 starts third high-pressure pump, and material is sprayed into airslide disintegrating mill (4) by third air jet pipe (42)
Interior and internal material collides, and then stops third high-pressure pump；Step 7 repeats step 3 to six, and repetition time 10-70 divides
Clock, while starting supersonic generator (7), the frequency of ultrasonic wave is 20k-50kHz；Step 8, material transfer portion will be from dischargings
Material transportation that (41) are collected is managed to finished bin, the material in finished bin is a nanometer Glucomannan.
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| CN107163156B true CN107163156B (en) | 2019-07-09 |
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| CN110905466B (en) * | 2019-11-20 | 2022-05-20 | 浙江工业大学 | Method for increasing yield and improving recovery ratio of biological nano-emulsion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735791A (en) * | 2009-11-11 | 2010-06-16 | 天津大学 | Konjac glucomannan water-base fracturing fluid as well as preparation method and gel breaking method thereof |
| WO2013051146A1 (en) * | 2011-10-07 | 2013-04-11 | 株式会社 荻野商店 | Method for producing depolymerized konjak glucomannan and depolymerized konjak glucomannan obtained thereby |
| CN103102430A (en) * | 2013-01-22 | 2013-05-15 | 广州城市职业学院 | Method for synergistically preparing konjac glucomannan with medium-polymerization degree |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735791A (en) * | 2009-11-11 | 2010-06-16 | 天津大学 | Konjac glucomannan water-base fracturing fluid as well as preparation method and gel breaking method thereof |
| WO2013051146A1 (en) * | 2011-10-07 | 2013-04-11 | 株式会社 荻野商店 | Method for producing depolymerized konjak glucomannan and depolymerized konjak glucomannan obtained thereby |
| CN103102430A (en) * | 2013-01-22 | 2013-05-15 | 广州城市职业学院 | Method for synergistically preparing konjac glucomannan with medium-polymerization degree |
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