CN102575515A - Composition and method for producing an ultra-lightweight ceramic proppant - Google Patents
Composition and method for producing an ultra-lightweight ceramic proppant Download PDFInfo
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Abstract
An ultra-lightweight, high strength ceramic proppant made from mixture of naturally occurring clays, preferably porcelain clay, kaolin and/or flint-clay, earthenware clay or other naturally occurring clays having an alumina content between about 5.5% and about 35%. The proppant has an apparent specific gravity from about 2.10 to about 2.55 g/cc, and a bulk density of from about 1.30 to about 1.50 g/cc. This ultra-lightweight proppant is useful in hydraulic fracturing of oil and gas wells, and has greater conductivity than sand at pressures up to 8,000 psi as measured by Stim-Lab after 50 hours and 275 DEG F on Ohio Sandstone, in the presence of deoxygenated aqueous 2% solution of KCI.
Description
Background
Fracturing is a kind of technical operation that is used to improve oil and natural gas output.This technology is usually directed to two steps.At first, through forming the crack, thereby allow that fracturing fluid gets into and gull to be enough to make speed that the stratum splits and pressure in well, to inject fracturing fluid.Secondly, inject in the stratum Selid propping agent (propping agent) or proppant (proppant) with " propping up (prop) " crack and be that oil and natural gas provides flow-guiding channel.Oil-gas reservoir with low-permeability needs fracturing usually so that they are increased economic efficiency.
Can use various dissimilar materials as proppant, for example fracturing sand, coated sand and artificial porcelain granule proppant, material chosen depends on the type of stratum permeability or required granule strength.Good proppant must have enough compressive strength in case crushed by the clossing pressure on stratum.The oil gas well is dark more, needs the more proppant of high compressive strength more.Because the fracturing sand source is extremely extensive and cost is low, so the proppant that the most often uses is a fracturing sand.Yet when using than the depths on the stratum, because bigger clossing pressure is arranged, fracturing sand does not have enough compressive strength, and the water conservancy diversion permeability of fracturing sand is not enough usually.
In the oil gas well greater than 15,000 feet well depths, usually the sintered bauxite proppant is used in suggestion, and a kind of proportion is about 3.50g/cc, has the high density proppants of about 83% alumina content.
Have found that middle density proppant (for example proportion is about between between the 3.10g/cc-3.45g/cc) has enough intensity and water conservancy diversion permeability under moderate depth and pressure, usually be used to be about the oil gas well between 8,000 feet to about 12,000 feet.
Yet high density and middle density proppant need large-scale pumping equipment, high viscosity fracturing fluid and high pumping rate keeping proppant at suspended state during fracturing operation, thereby on FLUID TRANSPORTATION and pumping equipment, cause excessive wearing and tearing more easily.
Consider the shortcoming of high density and middle density proppant, from the eighties in 20th century, the scientific research personnel constantly studies and uses the material that contains than al suboxide content to obtain light density and the proppant with enough anti-pressure abilities.In addition, increasing diminishing resistance fracturing fluid and fractured horizontal well all need be used light density ceramic proppant.
In the United States Patent(USP) No. of authorizing Lunghofer 4,522,731 and United States Patent(USP) No. 5,120,455, described a kind of low-density propping agent, this proppant use alumina content is 50% kaolin.This low-density propping agent has the proportion less than 3.0g/cc.
In the United States Patent(USP) No. of authorizing Sweet 5,188,175, described another kind of low-density propping agent with proportion between the 2.20g/cc to 2.60g/cc, it is the raw material between 25% to 40% that this proppant uses alumina content.
A kind of proppant that alumina content is about the less dense between 40% to 60% that has that is used for shallow oil gas well has been described in the United States Patent(USP) No. of authorizing Cannan 7,036,591.For obtaining the proportion of about 1.60g/cc to about 2.10g/cc, the sintering time of raw material will be less than 30 minutes, makes proppant under the situation of incomplete densified sintering product, makes proppant particles obtain crystallization.
Because the degree of depth of most of fracturing operations is superficial, in this scope, all usually uses fracturing sand.People are desirable to provide a kind of can be made by the clay of natural weathering economy, alumina content lower (for example alumina content less than 25%), when low or moderate depth are used, have the light density proppant than the bigger flow conductivity of fracturing sand.
The alumina content that reduces particle can reduce its density usually.Yet when alumina content became low, the intensity of proppant tended to become a problem.Therefore, in the industry a target is a kind of low-density propping agent of not sacrificing intensity of exploitation.
Ultra-low-density proppant of the present invention uses the clay (for example china clay, kaolin (or flint clay)) of the natural weathering more more economical than bauxite as main raw material(s).Therefore, each pound proppant has lower cost of manufacture.In addition, compare with bauxite, the clay source of natural weathering is wider.
In addition, in fracturing, from the angle of End-Customer, compare with high density or middle density proppant, the ultra-low-density proppant has lower density.So for certain support operation, only still less the ultra-low-density proppant of weight is filled the crack in the stratum.Proppant is often sold by weight, so this is to use one of significant advantage of ultra-low-density proppant.
Other advantages of ultra-low-density proppant comprise: compare with high density or desired those conditions of middle density proppant; The ultra-low-density proppant can use the fracturing fluid than low-viscosity; So that use more economical pumping rate, so that form lower wearing and tearing on FLUID TRANSPORTATION and the pumping equipment.
Invention is summed up
The invention discloses the ultra-low-density proppant that a kind of utilization is processed by the clay of natural weathering; The alumina content of the clay of this nature weathering is about between 5.5% to 35%; More satisfactory is between 5.5% to 25%, preferably between 14% to 25%.Proppant of the present invention has the proportion that is about between between the 2.10g/cc to 2.55g/cc, and more satisfactory is to be about between between the 2.30g/cc to 2.50g/cc; And be about between the bulk density between the 1.30g/cc to 1.50g/cc, more satisfactory is between between the 1.30g/cc to 1.40g/cc.U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8; The KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.
In a kind of specific embodiment, proppant of the present invention is by comprising between the china clay between 5% to 85%, processing between the mixture of kaolin between 5% to 85% and the potter's clay between 5% to 30%.This mixture alumina content is about between 5.5% to 35%, and is more satisfactory between 5.5% to 25%, preferably between 14% to 25%.
In some more desirable embodiments, proppant of the present invention has the silica (SiO between 69.5% and 89.5%
2) content, this content is preferably between 69.5% and 81.5%.
The present invention further discloses a kind of spheric granules of sintering, the Krumbein/Sloss circularity and the sphericity index of this spheric granules have 0.8 at least.The alumina content of said particle is about between 5.5% to 35%, and more satisfactory is between 5.5% to 25%, preferably between 14% to 25%.Of the present invention have the proportion that is about between between the 2.10g/cc to 2.55g/cc, and more satisfactory is between between the 2.30g/cc to 2.50g/cc; And be about between the bulk density between the 1.30g/cc to 1.50g/cc, preferably between between the 1.30g/cc to 1.40g/cc.
This ultra-low-density proppant can be applicable in fracturing and the gravel pack, is used for the fracturing sand control at the oil gas well.U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8; The KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.
For obtaining the maximum intensity of proppant particles, through tunnel cave or rotary kiln sintered, sintering time is about between 75 minutes to 960 minutes, preferably is about between 120 minutes to 720 minutes with raw material.Usually, sintering temperature is about between 1150 ℃ to 1380 ℃, preferably between 1200 ℃ to 1320 ℃.
The present invention further discloses a kind of method of pressure break subsurface formations, this method comprises: fracturing fluid is injected this stratum with speed and the pressure that is enough to form crack in the stratum, and in the crack, inject the fracturing fluid that comprises the present invention's proppant.
The specific embodiment
The ultra-low-density proppant graininess of processing by the clay mixture of natural weathering among the present invention spherical in shape; Alumina content is for being about between 5.5% to 35% in this mixture; More satisfactory is between 5.5% to 25%, preferably between 14% to 25%.Proppant of the present invention has the proportion that is about between between the 2.10g/cc to 2.55g/cc, preferably between between the 2.30g/cc to 2.50g/cc; And be about between the bulk density between the 1.30g/cc to 1.50g/cc, preferably between between the 1.30g/cc to 1.40g/cc.U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8; The KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.All used percentages all are percentage by weights among the present invention.
In a specific embodiment, proppant of the present invention can be by comprising between the china clay between 5% to 85%, processing between the mixture of kaolin between 5% to 85% and the potter's clay between 5% to 30%.The alumina content of this mixture is about between 5.5% to 35%, and more satisfactory is between 5.5% to 25%, preferably between 14% to 25%.
Raw material
According to the present invention, a kind of above-mentioned raw materials is china clay (porcelain clay).China clay is a kind of fine earth that is white in color usually, is formed by alumina mineral (for example, feldspar or porcelain stone) weathering.The toughness of china clay, intensity and translucence mainly are owing to producing at these high temperature lower-glass and the formation of mineral mullite in sintered body.China clay has less than 20% alumina content with greater than 65% dioxide-containing silica usually.Percentage is represented with dry weight here.
Being used for second kind of raw material of the present invention is potter's clay (earthenware clay).Potter's clay has plasticity and viscosity when humidity, but when roasting, can become hard.When mixing with special ratios with water, potter's clay has than china clay and the better plasticity of kaolin.When roasting in kilns is dry, because permanent physics and chemical reaction are arranged, it is hard that potter's clay can become.Except other changed, these physical-chemical reactions can make potter's clay be transformed into firm ceramic materials.Because these characteristics, especially plasticity, so potter's clay is a kind of good raw material of proppant semiproduct that are used to make.Potter's clay has less than about 25% alumina content with greater than about 60% dioxide-containing silica usually.
The third main raw material(s) is kaolin (kaolin).Kaolin has about 40% alumina content and about 45% dioxide-containing silica usually.In chemical compound, kaolin is (Al by the mineral molecular formula mainly
2O
32SiO
22H
2O) kaolinite weathering forms.Kaolin is a kind of high refractory clay that is higher than 1700 ° of C fusing points that has.But when using separately, kaolin is owing to its relatively poor plasticity is difficult to form particle shape; Also because its high refractoriness is difficult to form hard, fine and close particle through roasting.Kaolin uses seldom separately in making proppant.Therefore, must in kaolin, add china clay and potter's clay and make hard, the fine and close required sintering temperature of proppant to increase its plasticity and to be reduced to.
Used china clay, potter's clay and kaolin originates from Fujian China province Ningde City bowl kiln (in this patent, being defined as " Ningde china clay ", " Ningde potter's clay " and " Ningde kaolin " respectively) among the present invention.China clay, potter's clay and kaolinic another source of being fit to this proppant of making are depressed place, Fujian China province Fu'an City gulf (in this patent, being defined as " Fuan china clay ", " Fuan potter's clay " and " Fuan kaolin " respectively).Ningde and Fuan all are positioned at and have long making family expenses and the historical China of industrial ceramic product.For example, the bowl kiln, the literal meaning is " doing the kiln of bowl ", is famous to make various household utensils (for example bowl, urn and pottery etc.).The predominant use of Fuan clay is to produce the various products that use in pottery, refractory brick and the metal-processing industry, for example, and crucible, saggar, retorts bottle etc.The weight of the free sand in Ningde and Fuan clay (promptly quartzy) is less than 2% (hereinafter being expressed as " w/o ").
In described proppant of the present invention, kaolin can replace with flint clay.Flint clay is a kind of calcination seat clay with high refractoriness.Flint clay comprises higher silica and alumina content, has the impurity that few as much as possible meeting reduces the flint clay fusing point, for example lime, magnesia, soda and potash.Flint clay has about 45% alumina content and usually greater than about 40% dioxide-containing silica.
Because kaolin (or flint clay) has sufficiently high alumina content, can with its mix with china clay of mainly forming by silica and potter's clay with acquisition have alumina content between 5.5% to 35%, more satisfactory be between between 5.5% to 25%, be preferably the mixture between 14% to 25%.
In an instantiation, the percentage by weight of raw mix is following:
● china clay: 5%-85%
● kaolin (and/or flint clay): 5%-85%
● potter's clay: 5%-30%
The major impurity of china clay, potter's clay and kaolin (or flint clay) is titanium, iron compound and a spot of potassium and magnesium compound.
Optimize in the instance at some, raw mix can further comprise the strength additive that is selected from ilmenite concentrate, zircon sand, alumina or its combination.The percentage by weight of strength additive is to be about between about 5% to 10%.
Disclosed ultra-low-density proppant also can be processed by the clay of other natural weathering among the present invention, and the alumina content of these clays is about between 5.5% to 35%, and more satisfactory is between 5.5% to 25%, preferably between 14% to 25%.
Term is introduced
In the present invention, term " fracturing sand " is used in reference to high-quality " Ottawa " sand with 20/40 sieve mesh.
The term that uses among the present invention " flow conductivity " is meant the product of the permeability of crack width and proppant pack.Under the specified conditions of stress, temperature, corrosive atmosphere and time, the flow conductivity of proppant is a most important index of weighing the proppant quality.
The permeability that the flow conductivity of proppant is defined as proppant pack multiply by the width in supported crack.Usually applying unit millidarcy-foot (" md-ft ") expression.
The term " permeability " that here uses is to weigh medium is carried fluid through the space, hole ability.Usually, flow conductivity or permeability are preferably in many indexs of reflection proppant anti-pressure ability, and can be provided at the many valuable information of proppant performance in the subsurface formations.
Used term " sphericity " is used to weigh proppant particles and to what extent approaches spheroid form among the present invention.Term used herein " circularity " is the measurement to the relative acutance or the proppant curvature of proppant corner angle.Since 1963, be widely used in by the chart of Krumbein and Sloss exploitation sphericity and circularity have been estimated.Should confirm, write down the average of sphericity and circularity and calculating, record sphericity and the circularity of each sample.
Term " proportion " is the weight (gram/cubic centimetre) of the per unit volume (comprising internal void) of particle.Provided the proportion of the proppant of selling on the multiple market in the Table I.
Table I
| Commercial proppant | Bulk density (g/cc) | Proportion (g/cc) |
| 20/40 high-density porcelain granule support agent | 2.02 | 3.50 |
| Density ceramic proppant in 20/40 | 1.88 | 3.25 |
| 20/40 light density ceramic proppant | 1.57 | 2.71 |
| 20/40 coated sand | 1.60 | 2.61 |
| 20/40 Ottawa fracturing sand | 1.60 | 2.62 |
Term " bulk density " is the per unit volume weight (gram/cubic centimetre) of (comprising the void space between the volume endoparticle of being considered).Provided the bulk density of proppant on sale on the multiple market in the Table I.
Usually, preparation method of the present invention relates to 7 steps: raw material calcination, mixing and grinding, grain forming, drying and preheating, sintering, cooling and final sizing.Hereinafter technology is described in detail.
The raw material calcination
Before forming particle, can carry out calcination or not carry out calcination kaolin.China clay and potter's clay need not carry out calcination.If kaolin is carried out calcination, calcination temperature should be at about about 1100 ℃.So high calcination temperature, be not only one in order to cause the Technology for Heating Processing of thermal decomposition (for example remove organic matter and remove water of hydration and moisture), and be for forming the phase transformation technology that mullite or cristobalite carry out.
Mix and grinding
Kaolin should be with calcination and the china clay of milling and potter's clay mix.The alumina content of mixture should be less than 35%.The alumina content of mixture less than 35% condition under, before granulation, be ground into the dry powder that average particle size particle size is about 3-5 micron.
Granulation
Granulation can be used many diverse ways.These methods are well-known in the proppant manufacturing, and disclosed a kind of method of using sponging granulator or fluid bed in No. 731 for example, is arranged at United States Patent (USP) the 4th, 522.Here, we put down in writing a kind of method of using comminutor.
Granulation machine that honest ceramic device company (Yixing Zhengda Ceramic Equipment) obtains from Yixing or comminutor can rotate with the speed that about per minute 10-120 changes.Then, the clay powder of the drying that warp ground is added constantly and is mixed, up to the semiproduct particle formation of required size.When only under suitable rotating speed and time, adding water and the powder of suitable quantity, this technology could produce smooth, spherical, solid proppant semiproduct particle.
According to the present invention, behind sintering, proppant is the particle of color even and solid sphere.
Beat allly be, make proppant of the present invention, need not add any jointing material or adhesive.According to Krumbein/Sloss circularity and sphericity table, circularity and sphericity can reach about 0.8 at least.
Drying and preheating
Then, spheric granules is taken out and is dried to from comminutor make free water content less than 3%.Suitable baking temperature is between about 300 ℃ to about 400 ℃ and be between 30 minutes to 45 minutes drying time.After drying, spheric granules is separated into the size of different needs through screening.The particle of the size of not satisfying the demand will be sifted out and recycle.
Sintering
With behind the particle drying of satisfying the demand after the screening in the size range soon, they are carried out sintering in rotary kiln or tunnel cave.Sintering time in rotary kiln or the tunnel cave and temperature are very crucial.Many factors decision sintering times and temperature are arranged, for example the material volume in raw material mineralogical character, particle size, semiproduct size and the kiln after milling.
1) through rotary kiln sintered
Usually, sintering temperature is for being about between 1150 ℃ to 1380 ℃, and more satisfactory is between 1200 ℃ and 1320 ℃.Sintering time is about between 75 minutes to 960 minutes, and more satisfactory is between 120 minutes to 720 minutes.
Have found that the intensity of particle when the intensity of particle was 35 minutes greater than sintering time when sintering time was 120 minutes.
In addition, find that according to applicant of the present invention if sintering temperature is too high, for example be higher than 1450 ℃, the moulding of particulate is relatively poor, and because alumina (Al
2O
3) content is low, particle will adhere to each other.
2) pass through tunnel kiln sintering
Tunnel cave is a kind of dolly repulsive-type maglev continuous kiln, is made up of preheating zone, dry section, firing zone and cooling zone.It is applicable to a large amount of production ceramsite propping agents.It is a kind of production method of streamline.The carrier loader of loaded with proppant semiproduct particle is every to be imported and shifts out from an other end from tunnel cave one end at a distance from about one hour.The carrier loader that thrust unit progressively will newly import and other carrier loaders before this carrier loader push the length of a carrier loader of tunnel cave.Thrust unit is then return so that wait the next carrier loader of packing into.The sintering zone is positioned at the central authorities in tunnel, and several weeks, several months or several years holding temperature are till shutting down according to maintenance requirement.
Compare with rotary kiln, in tunnel cave, making proppant has a plurality of advantages.Processes such as at first, preheating, drying, sintering, cooling are (closed system) the inside in the tunnel all.This tunnel structure can absorb and keep heat, and is easier to be provided with temperature and control sintering time.The second, because it is a kind of continued operation, so proppant steady quality and be easy to improve.The 3rd, because particle almost is in " static " position during heating and sintering, that particle can keep is smooth and spherical.At last, compare with rotary kiln, output control is more flexible, can according to the market demand from every month 3,000 tons adjust to every month 6,000 tons.
Be similar to rotary kiln technology, preheating in the tunnel cave and baking temperature are for being about between 300 ℃ to 400 ℃, and preheating and drying time are for being about between 30 minutes to 45 minutes.
After dry and preheating, the semiproduct particle gets into the sintering zone that is positioned at tunnel central authorities.Usually, sintering temperature is for being about between 1150 ℃ to 1380 ℃, and more satisfactory is between 1200 ℃ to 1320 ℃.Sintering time be about between 75 minutes to 960 between, more satisfactory is about between 120 minutes to 720 minutes.Satisfying under the above condition, particle complete densification of meeting and moulding are good.
In addition, the applicant finds that if sintering temperature is too high, for example be higher than 1450 ℃, molding particles is relatively poor, and because alumina content (Al
2O
3) content is low, particle will adhere to each other.
Cooling and screening
In rotary kiln or tunnel cave, behind the sintering, particle is cooled to the room temperature about 28 ℃, and is sized to desired final size once more, for example 20/40 or 40/70 mesh size.
Behind sintering, particle is sized to desired final size once more.For example, mesh size is 40/70 proppant, and wherein the size of 90% particle is between 0.212 μ m and 0.425 μ m.
The proppant of the preferred embodiment of the present invention have between between 2.10 to 2.55g/cc, have the proportion (according to the method for testing of ISO 13503-2 standard) between 2.30 to 2.55g/cc under the more satisfactory situation, and between 1.30g/cc to approximately between the 1.50g/cc, have the bulk density between 1.30 to 1.40g/cc under the more satisfactory situation.
Proppant particles color even among the present invention.
Following specific embodiment is further set forth the present invention.In these instantiations, unless otherwise prescribed, all percentages all are percentage by weights.
Specific embodiment 1
The mixture of being made up of the kaolin of 52% china clay and 26% added in 22% the potter's clay powder.At this moment kaolin is by calcination and through grinding, then with not annealed china clay and potter's clay powder mixes.The all Ningde City bowl kiln supplies of all raw materials from Chinese Fujian Province.
As a specific embodiment of the present invention, the alumina content of gained mixture is 23.36%.Concrete chemical compound is following:
| The chemical compound of material | Mixture (%) |
| Al 2O 3 | 23.36 |
| SiO 2 | 70.68 |
| Fe 2O 3 | 2.04 |
| K 2O | 2.11 |
| TiO 2 | 1.16 |
| MgO | 0.30 |
| CaO 2 | 0.15 |
| Na 2O | 0.18 |
| Other | 0.02 |
With the granulation in the comminutor that the honest ceramic device in Yixing company (Yixing Zhengda Ceramic Equipment) produces of above mixture.The speed of this comminutor is approximately per minute 25 changes.For the proppant of 40/70 sieve mesh, the granulation time is approximately 75 minutes.
The particle of gained is dry under with 350 ℃ temperature in drying stove (or dryer), then at 1275 ℃ of sintering temperatures.
The mesh size of gained proppant is 40/70 in the specific embodiment 1, and by being positioned at Duncan, the STIM-Lab laboratory of the Core Laboratories Company of Oklahoma makes an experiment.The result of the test of STIM-Lab shows that bulk density is 1.34g/cm
3, proportion is 2.42g/cm
3, the percentage of damage under 7500psi pressure is 2.7%, 10, the percentage of damage under the 000psi pressure is 6.7%.
Below be the properties of product of STIM-Lab based on 40/70 proppant of ISO 13503-2 experimental technique test:
| Project | Result of the test | Unit |
| Sphericity | 0.9 | Inapplicable |
| Circularity | 0.9 | Inapplicable |
| Acid solubility | 4.0 | ％ |
| Turbidity | 18 | FTU |
| Bulk density | 1.34 | g/cm 3 |
| Proportion | 2.42 | g/cm 3 |
| Compression test, 7500psi | 2.7 | ％ |
| Compression test, 10,000psi | 6.7 | ％ |
STIM-Lab has developed the generally accepted test method that is used for confirming proppant flow conductivity and permeability in the industry.
After the STIM-Lab test, find that proppant of the present invention has than has the higher flow conductivity of fracturing sand of bigger proportion.For example; U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8, the KCl solution of the clossing pressure of 000psi and 2% deoxygenation is through the temperature of 50 hours and 275 ° of F); The flow conductivity of proppant of finding 40/70 sieve mesh of preferred specific embodiment of the present invention is at least 560md-ft, is at least 580md-ft under the more satisfactory situation.
Below be the step that is used for measurement flow conductivity of the present invention and Test Liquid Permeability of Core:
1. the equipment that is used to measure flow conductivity and Test Liquid Permeability of Core comprises:
● have 75 tons of Dake forcing presses of gas-oily booster.The API SS316 or the Monel K-5000 diversion chamber that have 10 square inches of fluid areas.
● be used for 40: 1 pressure sensors of Rosemont (intelligence series) of gaging pressure decline and speed, use 1/4 inch pipeline detection, use the calibration of intelligence system computer, be set in 0-5 inch range hydraulic pressure.
● two gallons of nitrogen drive fluid storage tank, are filled with the KCl of 2% nitrogen deoxidation.
● be used to measure the inside callipers and the clamp of width.
● deal with data is also calculated flow conductivity and the ibm personal computer of permeability.
● two 10 square inches Ohio sandstone.
● the API diversion chamber that proppant sample to be measured is housed.Proppant and blading levelling.
2. the proppant sample is placed between the rock core plate, and becomes the part of the conduction pipe of forming by 4 diversion chamber.
3. diversion chamber being stacked on error from the top to the bottom is in 0.002 inch scope, and is placed between the platen of Dake forcing press.Pressure is increased to 500psi, and with this system air emptying and under 70-75 ° of F temperature water fill with.
4. in case after diversion chamber is filled with by liquid, clossing pressure is increased to 1000psi with the speed of per minute 100psi.Shown in tables of data, make proppant reach balance.
5. measuring rate, pressure reduction and mean breadth under each pressure are so that calculate flow conductivity and permeability.Get 5 measured values and average to obtain flow conductivity.Use the LiquiFlow measuring device to measure flow, the LiquiFlow measuring device uses Mettler to calibrate to 0.01ml/min.Use Darcy's law to calculate to confirm flow conductivity and permeability.
6. test temperature is increased to 250 ° of F and make it keep stable.Before increasing clossing pressure, temperature was kept 12 hours under 250 ° of F.
7. shown in tables of data, under room temperature and 250 ° of F, obtain 1, the flow conductivity of proppant and permeability under the 000psi clossing pressure.
8. the speed with per minute 100psi increases clossing pressure, increases progressively 1 at every turn, and 000psi repeats above-mentioned measuring method.
9. 2, the flow conductivity of continuous monitoring proppant and permeability are 50 hours under 000psi and the 250 ° of F.
10. 4, the flow conductivity of continuous monitoring proppant and permeability are 50 hours under 000psi and the 250 ° of F.
11. 6, the flow conductivity of continuous monitoring proppant and permeability are 50 hours under 000psi and the 250 ° of F.
12. 8, the flow conductivity of continuous monitoring proppant and permeability are 50 hours under 000psi and the 250 ° of F.
For example; U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8, the KCl solution of the clossing pressure of 000psi and 2% deoxygenation is through the temperature of 50 hours and 275 ° of F); The flow conductivity of proppant of finding 40/70 sieve mesh of preferred specific embodiment of the present invention is at least 560md-ft, is at least 580md-ft under the more satisfactory situation.(report SL8674).
Specific embodiment 2
Repeat raw material and preparation method identical described in specific embodiment 1.Specifically, the size of proppant be 30/50,90% proppant size between 0.300 μ m and 0.600 μ m.For obtaining the semiproduct particle of desired size, the about per minute 25 of comminutor rotating speed changes, and the time of granulation is approximately 90 minutes.
Hereinafter is the properties of product of STIM-Lab based on the proppant of 30/50 sieve mesh of ISO 13503-2 measurement of test method:
| Project | Result of the test | Unit |
| Sphericity | 0.8 | Inapplicable |
| Circularity | 0.8 | Inapplicable |
| Acid solubility | 4.0 | ％ |
| Turbidity | 8 | FTU |
| Bulk density | 1.31 | g/cm 3 |
| Proportion | 2.41 | g/cm 3 |
| Compression test, 7,500psi | 7.1 | ％ |
Use 30/50 proppant to repeat identical STIM-Lab flow conductivity and the characteristic test described in the specific embodiment 1.
Specific embodiment 3
The mixture of being made up of the kaolin of 65% china clay and 15% added in 20% the potter's clay.At this moment kaolin is not by calcination.As a specific embodiment of the present invention, the alumina content of mixture is 19.05%.Detailed chemical compound is following.
| The chemical compound of material | Mixture (%) |
| Al 2O 3 | 19.05 |
| SiO 2 | 71.60 |
| Fe 2O 3 | 2.23 |
| K 2O | 2.08 |
| TiO 2 | 1.98 |
| MgO | 1.93 |
| CaO 2 | 0.45 |
| Na 2O | 0.23 |
| Other | 0.45 |
Repetition is manufacturing approach described in specific embodiment 1.In specific embodiment 3 gained proppant sizes is 40/70 sieve mesh, is detected by PetroChina Company Limited. product quality supervision and inspection center.The testing result of PetroChina Company Limited. shows that bulk density is 1.30g/cm
3, proportion is 2.40g/cm
3, 7, the 500psi percentage of damage is 4.6%.
Below be PetroChina Company Limited. product quality supervision and inspection center test for data summary, test procedure is based on ISO 13503-2 test method:
Be the flow conductivity test of PetroChina Company Limited.'s product quality supervision and inspection center test here:
Specific embodiment 4
Repetition is in raw material and manufacturing approach described in the specific embodiment 3.The gained mixture still has 19.05% aluminum content.Specifically, proppant is 20/40 mesh size, 90% proppant size between 0.425 μ m and 0.850 μ m.For obtaining the semiproduct particle of desired size, comminutor speed is approximately per minute 25 changes, and the granulation time is approximately 105 minutes.
Below be the data summarization of 20/40 proppant:
| Project | Result of the test | Unit |
| Sphericity | 0.9 | Inapplicable |
| Circularity | 0.9 | Inapplicable |
| Acid solubility | 4.2 | ％ |
| Bulk density | 1.30 | g/cm 3 |
| Proportion | 2.40 | g/cm 3 |
| Compression test, 5,000psi | 3.8 | ％ |
| Compression test, 7,500psi | 9.5 | ％ |
Specific embodiment 5
The mixture of being made up of the flint clay of 24% china clay and 59% is added in 12% potter's clay and 5% the ilmenite concentrate as additive.Here, ilmenite concentrate can be substituted by zircon sand, alumina or its composition.
As a specific embodiment of the present invention, the alumina content of gained mixture is 34.18%.Detailed chemical compound is following.
| The chemical compound of material | Mixture (%) |
| Al 2O 3 | 34.18 |
| SiO 2 | 57.23 |
| TiO 2 | 3.38 |
| Fe 2O 3 | 2.08 |
| K 2O | 1.01 |
| MgO | 0.47 |
| CaO 2 | 0.40 |
| Na 2O | 0.91 |
| Other | 0.34 |
Repetition identical manufacturing approach described in embodiment 1 is made the proppant of 40/70 sieve mesh.The proppant volume density of gained 40/70 sieve mesh is 1.40g/cm
3, proportion is 2.46g/cm
3, be 7 at clossing pressure, the percentage of damage under the 500psi is 2.36%, is 10 at clossing pressure, the percentage of damage under the 000psi is 5.80%.
Below be the properties of product data summarization of 40/70 proppant:
| Project | Result of the test | Unit |
| Sphericity | 0.8 | Inapplicable |
| Circularity | 0.8 | Inapplicable |
| Acid solubility | 5.1 | ％ |
| Turbidity | 15 | FTU |
| Bulk density | 1.40 | g/cm 3 |
| Proportion | 2.46 | g/cm 3 |
| Compression test, 7,500psi | 2.36 | ％ |
| Compression test, 10,000psi | 5.8 | ％ |
According to observations, after adding strength additive, the proppant of 40/70 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 3% under the 500psi, is 10 at clossing pressure, has the percentage of damage less than about 6% under the 000psi.
Sum up
The proppant particulate color even of specific embodiment 1 to 5.The properties of product data of result of the test are following:
The proppant of disclosed 40/70 sieve mesh is 7 at clossing pressure among the present invention, has the percentage of damage less than about 5% under the 500psi, is 10 at clossing pressure, has the percentage of damage less than about 10% under the 000psi; The proppant of 30/50 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 10% under the 500psi, is 10 at clossing pressure, has the percentage of damage less than about 15% under the 000psi; The proppant of 20/40 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 15% under the 500psi, is 10 at clossing pressure, has the percentage of damage less than about 20% under the 000psi.
In fact, the industry peer carries out trickle change to material content or proppant manufacturing approach and can repeat the present invention.These are with consistent what is claimed is of the present invention's proposition for the change of material and manufacturing approach in itself, and are contained by the present invention.
Claims (29)
1. ultra-low-density proppant; This proppant is processed by the raw mix that comprises china clay, potter's clay and kaolin (and/or flint clay); It is characterized in that; The percentage by weight of china clay be about between between 5% to 85%, the percentage by weight of kaolin (and/or flint clay) is about between 5% to 85%, and the percentage by weight of potter's clay is about between 5% to 30%.
2. proppant as claimed in claim 1 is characterized in that said proppant has the alumina content that is about between 5.5% and 35%.
3. proppant as claimed in claim 2 is characterized in that said proppant has the alumina content that is about between 5.5% and 25%.
4. proppant as claimed in claim 3 is characterized in that said proppant has the alumina content that is about between 14% and 25%.
5. proppant as claimed in claim 3 is characterized in that, said proppant has the silica (SiO that is about between 69.5% and 89.5%
2) content.
6. proppant as claimed in claim 4 is characterized in that, said proppant has the silica (SiO that is about between 69.5% and 81.5%
2) content.
7. like each described proppant in the claim 1 to 6, it is characterized in that said proppant has the proportion that is about between between the 2.10g/cc to 2.55g/cc, and be about bulk density between 1.30g/cc to 1.50g/cc.
8. proppant as claimed in claim 7 is characterized in that said proppant has the proportion between 2.30g/cc and 2.50g/cc.
9. proppant as claimed in claim 7 is characterized in that said proppant has the bulk density between 1.30g/cc and 1.40g/cc.
10. like each described proppant in the claim 1 to 9; It is characterized in that; U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone, 8, the KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.
11. proppant as claimed in claim 1 is characterized in that, the proppant of 40/70 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 5% under the 500psi, and is 10 at clossing pressure, has the percentage of damage less than about 10% under the 000psi.
12. proppant as claimed in claim 1 is characterized in that, the proppant of 30/50 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 10% under the 500psi, and is 10 at clossing pressure, has the percentage of damage less than about 15% under the 000psi.
13. proppant as claimed in claim 1 is characterized in that, the proppant of 20/40 sieve mesh is 7 at clossing pressure, has the percentage of damage less than about 15% under the 500psi, and is 10 at clossing pressure, has the percentage of damage less than about 20% under the 000psi.
14., it is characterized in that the proppant of describing is the particle of color even and solid sphere like the described proppant of claim 1.
15., it is characterized in that said raw mix also comprises mineral such as being selected from ilmenite concentrate, zircon sand, alumina like each described proppant in the claim 1 to 14, or the strength additive that forms by these mineral assemblages.
16. ultra-low-density proppant; This proppant has the proportion that is about between between the 2.10g/cc to 2.55g/cc; And be about between the bulk density between the 1.30g/cc to 1.50g/cc; It is characterized in that said proppant is processed by the mixture of the clay of natural weathering, alumina content is for being about between 5.5% to 35% in the said mixture.
17. proppant as claimed in claim 16; It is characterized in that; U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone, 8, the KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.
18., it is characterized in that the alumina content in the said mixture is about between 5.5% to 25% like claim 16 or 17 described proppants.
19. proppant as claimed in claim 18 is characterized in that, the alumina content in the said mixture is about between 14% to 25%.
20. proppant as claimed in claim 18 is characterized in that, the silica (SiO in the clay mixture of said natural weathering
2) content is about between 69.5% and 89.5%.
21. proppant as claimed in claim 19 is characterized in that, the silica (SiO in the clay mixture of said natural weathering
2) content is about between 69.5% and 81.5%.
22. proppant as claimed in claim 16 is characterized in that, said proppant is the particle of color even and solid sphere.
23. having on Krumbein/Sloss circularity and sphericity table, to measure to have at least, the spheric granules of a sintering, this spheric granules be about 0.8 circularity and sphericity.It is characterized in that the alumina content of said particle is for being about between 5.5% to 35%.
24. particle as claimed in claim 23 is characterized in that, said particle has the proportion that is about between between the 2.10g/cc to 2.55g/cc, and is about between 1.30g/cc to the bulk density between about 1.50g/cc.U.S. STIM-Lab laboratory is with their test method detection (this experimental technique employing Ohio sandstone; 8; The KCl solution of the clossing pressure of 000psi and 2% deoxygenation; Temperature through 50 hours and 275 ° of F), prove that this ultra-low-density proppant has than fracturing sand and has bigger flow conductivity.
25. particle as claimed in claim 24 is characterized in that, said particle has the alumina content that is about between 5.5% and 25%, and has the silica (SiO that is about between 69.5% and 89.5%
2) content.
26. particle as claimed in claim 25 is characterized in that, said particle has the alumina content that is about between 14% to 24%, and has the dioxide-containing silica that is about between 69.5% and 81.5%.
27. the method for a pressure break subsurface formations comprises: fracturing fluid is injected said stratum with speed and the pressure that is enough to form crack in the said stratum, and in said crack, inject the fracturing fluid that comprises any described proppant of claim 1 to 22.
28. method of making any said proppant in the claim 1 to 22; It is characterized in that; The high strength of proppant is to be controlled to be through the sintering time with sintering process to be about between 75 minutes to 960 minutes, and sintering temperature is controlled to be to be about between 1150 ℃ between 1380 ℃, obtains.
29. method as claimed in claim 28 is characterized in that, the said firing time of said sintering process is for being about between 120 minutes to 720 minutes, and said sintering temperature is for being about between 1200 ℃ to 1320 ℃.
Applications Claiming Priority (5)
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| US22856209P | 2009-07-25 | 2009-07-25 | |
| US61/228,562 | 2009-07-25 | ||
| CN2010101573464 | 2010-04-27 | ||
| CN201010157346.4 | 2010-04-27 | ||
| PCT/US2010/042980 WO2011014410A1 (en) | 2009-07-25 | 2010-07-23 | Composition and method for producing an ultra-lightweight ceramic proppant |
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| CN102575515B CN102575515B (en) | 2015-06-24 |
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| CN103666443A (en) * | 2013-12-13 | 2014-03-26 | 淄博嘉丰矿业有限公司 | Low-density ceramsite proppant and preparation method thereof |
| CN108219768A (en) * | 2017-12-12 | 2018-06-29 | 常州莱尚纺织品有限公司 | A kind of ceramsite petroleum fracturing propping agents and preparation method thereof |
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| CN115180920A (en) * | 2022-08-09 | 2022-10-14 | 陕西延长石油压裂材料有限公司 | Ultralow-density ceramsite proppant and preparation method thereof |
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| CN109020600A (en) * | 2018-09-03 | 2018-12-18 | 深圳市绿洲生态科技有限公司 | A kind of ecology pearl and preparation method thereof |
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Address after: Sugar City, Texas, USA Co-patentee after: Fujian Junjie new materials Polytron Technologies Inc Patentee after: American Roybo Co. Ltd. Address before: Sugar City, Texas, USA Co-patentee before: Junjie Porcelain Co., Ltd., Ningde Patentee before: American Roybo Co. Ltd. |
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