CN108136437A - Conductive supporting agent and production and preparation method thereof - Google Patents

Abstract

Disclose the method for manufacturing conductive supporting agent particle.This method can include preparing the slurry containing water, adhesive and salic raw material, by the slurry atomization into drop, and coat salic seed with drop to form multiple green pellets.Green pellets can be made to be contacted with the activated solution comprising at least one catalytically-active materials, to provide the activated green pellets for including at least one catalytically-active materials.This method can include being sintered activated green pellets to provide multiple proppant particles.Multiple proppant particles can be made to be contacted with the plating solution containing one or more conductive materials, to provide conductive supporting agent particle.

Description

Conductive supporting agent and production and preparation method thereof

Technical field

The embodiment of the present invention relates generally to architectonic hydraulic fracturing, more particularly relates to gas, oil or ground Conductive supporting agent in the hydraulic fracturing stimulation (stimulation) of heat reservori.

Background technology

In order to stimulate and more effectively from down-hole formation, particularly be produced with the stratum of low-porosity and/or hypotonicity Raw hydrocarbon, the pressure break on the hydrocarbon-containiproducts stratum induced (are known as " fracturing work ", " hydraulic fracturing " or referred to as " pressure break ") it is always common technology.In typical fracturing work, fluid is pumped to underground under high pressure, and stratum is caused to exist Wellbore is broken, and generates the high osmosis pipeline that hydrocarbon is promoted to enter wellbore.These fracturing works can be in level With deviate and vertical drilling in and in the interval of no cased well or across carrying out in the cased well of perforation.

For example, in the cased wellbores of vertical well, high-pressure fluid is by passing through the perforation of casing and surrounding cement to leave brill Hole, and lead to stratum breaking, usually (oil is wherein generally found on deeper stratum in thin, substantially vertical sheet-forming slit It is gentle) in be broken.The crack of these inductions is usually laterally extended quite remote distance from wellbore, into the stratum of surrounding, and Extend right up to crack reach be not easy on required pressure break interval and/or under the stratum that ruptures.In stratum it is maximum and The direction of minimum level stress determines the azimutal orientation of induced fractures.In general, if the fluid in pumped downhole (is sometimes referred to as For slurry) without the solid remained in crack, then when Fluid pressure relaxes, crack can re-close, and lose big portion Divide the benefit of catalytic gas.

These solids for being referred to as proppant are usually made of sand grains or ceramic particle, and for these solids to be pumped into The fluid of underground is generally designed to sticky enough so that when fluid underground moving and enter induction crack in when proppant Particle retaining clip band is in a fluid.Before the stratum produced fracture, also claimed in pumped downhole to fracturing fluid slurry Material for " demulsifier " reduces the viscosity of fracturing fluid after desired time delay so that these fluids are in production process In can easily be removed from crack so that proppant particles are stayed in position in the crack of induction, with Its closure is prevented, is flowed through wherein so as to be essentially prevented production fluid.

Proppant can also use low viscosity fluid in the fracturing operation for being referred to as " hydraulic pressure is split " or " slippery water pressure break " It is placed in inductivity crack.Fracturing fluid during hydraulic pressure is split is that have little or no polymer or the water of other additives.Water Pressure break is advantageous, because the cost of fluid used is relatively low.In addition, when using cross-linked polymer, it is necessary to make demulsifier effective Or fluid cannot be recycled from crack, so as to effectively limit the flowing of formation fluid.Because fluid is not crosslinked, therefore water Pressure break does not depend on the validity of demulsifier.

Common proppant includes naturally occurring husky, resin coating sand and ceramic proppant.Ceramic proppant is usual It is made of naturally occurring material, such as kaolin and bauxite clay, and mainly due to the pressure resistance of manufactured ceramics Degree and its highly spherical grain shape provide many advantages compared with the sand of husky or resin coating.

Although induced fractures are a very effective tools in oil-gas reservoir production, the stimulation that this process provides (volume increase) amount depends greatly on the ability for generating new crack or creation or the existing crack of extension and passes through It is appropriate to place proppant to maintain the ability being connect with crack.In the case of no suitably placement proppant, in waterpower pressure Splitting the crack generated in the process may be intended to be closed, so as to reduce the benefit of hydraulic fracturing processing.However, for detecting, It positions and is characterized in the placement of the proppant in the crack at wellbore distance apart from each other so as to confirm whether this placement closes Suitable reliable method is disabled.

The prior art of proppant recognition techniques is limited in (maximum 12 inches to 18 English away from the relatively short distance of wellbore It is very little) at.The presence of radioactivity and nonradioactive tracer and proppant currently used for speculating proppant in near-wellbore region.It needs It is best understood from placement of the proppant in the far-field region of hydraulic fracture.

Bartel, L.C., McCann, R.P., and Keck, L.J. are the 51st autumn technical conference and petroleum works It can exhibition (51st Annual Fall Technical Conference and Exhibition of Society of Petroleum Engineers) prepare potential gradient large hydraulic fracturing survey and draw and characterize in application (Use of potential gradients in massive hydraulic fracture mapping and Characterization), New Orleans, Oct 3-6,1976paper SPE 6090 summarizes large hydraulic fracturing survey Work before painting.In work before, two concentric circles of the voltage electrode around vertically fractured well at the earth's surface Between measure potential difference.Well is powered (energize) at the top of casing or the penetration of fracture.Apart from about 1 mile of crack well Remote Jing Chu establishes electrical ground.At that time, the fact that ground wire is as transmitting antenna is not accounted for.Contain for the water of fracture process There is potassium chloride (KCl) to improve its electric conductivity, and use non-conductive husky supporting crack.Use 1Hz repetition rate square wave inputs Current waveform, and only measure voltage difference amplitude.Using based on from casing and crack to the current leakage in the homogeneous earth The voltage of basic theories generates intended response.The result of field data and basic model is compared and shows may infer that Crack is orientated, but since the model does not account for the details in crack, other Cracks characters cannot be determined with basic model.

Currently used for detecting, positioning and characterizing the branch being located at cased wellbores in the hydraulic fracture for being more than a few inches of distances The method of support agent position is disabled, and this method will be beneficial.Therefore, it is necessary to can be detected in hydraulic fracture and The proppant particles of positioning.It is particularly desirable that obtain the branch for being suitable for strutting crack and be detected in crack over time Support agent particle.It also needs to obtain the economic means for manufacturing this detectable proppant particles.

Brief Description Of Drawings

By reference to the following description and drawings for being used to illustrate the embodiment of the present invention, the present invention can be best understood. In figure：

Fig. 1 is the schematic diagram for being used to be prepared the substantially system of the particle of spheroidal as described herein by slurry.

Fig. 2 is the flow chart for being coated electrolessly method for showing conductive material on proppant base material.

Fig. 3 is another flow chart for showing the alternative steps that are coated electrolessly method of the conductive material on proppant base material.

Fig. 4 is another schematic diagram for being used to be prepared the substantially system of the particle of spheroidal as described herein by slurry.

Fig. 5 is the another schematic diagram for being used to be prepared the substantially system of the particle of spheroidal as described herein by slurry.

Fig. 6 is the another schematic diagram for being used to be prepared the substantially system of the particle of spheroidal as described herein by slurry.

Fig. 7 is the another schematic diagram for being used to be prepared the substantially system of the particle of spheroidal as described herein by slurry.

Fig. 8 is the drippage casting (drip for being used to be prepared the substantially particle of spheroidal as described herein by slurry Cast) the schematic diagram of system.

Fig. 9 is used for as described herein by the another of the drippage casting system of the slurry preparation substantially particle of spheroidal Schematic diagram.

Figure 10 is the spray nozzle device for including being arranged on the drippage casting nozzle in processing nozzle (treatment nozzle) Diagram.

Figure 11 is the figure for another spray nozzle device for including being arranged on the drippage casting nozzle in the processing nozzle with entrance Show.

Figure 12 shows the vertical view of the spray nozzle device of Figure 11.

Figure 13 is vertical or deviated well geometric layout figure, wherein depicting modified electrical property and mechanical performance Earth stratum.

Figure 14 is the horizontal hole casing string across the hydrocarbon-containiproducts region installation with proppant filling crack Schematic diagram, wherein depicting modified electrical property and the earth stratum of mechanical performance.

Figure 15 is the schematic cross section of hydraulic fracturing mapping system, and which depict two be introduced into electric current in wellbore Embodiment is powered to wellbore on surface, and passes through the sedimentation bar near perforation in the wellbore and be powered via steel wire rope.

Figure 16 is the schematic diagram of hydraulic fracturing mapping system.

Figure 17 is the perspective illustration of hydraulic fracturing mapping system.

Figure 18 A are the schematic diagrames of insulating sleeve of electric pipe fitting.

Figure 18 B are the schematic diagrames of insulating sleeve of electric trunnion ring.

Figure 19 is the schematic diagram for measuring the test system of proppant resistance.

Figure 20 is the resistivity (Ohm-cm) of various proppant samples and the curve graph of confining pressure (psi).

Figure 21 is the resistance of the mixture for 20/40 sample of CARBOLITE 20/40 and standard ECONOPROP for being coated with aluminium The curve graph of rate (Ohm-cm) and confining pressure (psi).

Figure 22 is the resistance of the mixture for 40/80 sample of HYDROPROP 40/80 and standard HYDROPROP for being coated with aluminium The curve graph of rate (Ohm-cm) and confining pressure (psi).

Figure 23 is to be coated with the CARBOLITE 20/40 of nickel and be coated with the conductivity (west gate of the CARBOLITE 20/40 of copper Son/m) with the curve graph of pressure (psi).

Figure 24 is the conductivity (Siemens/m) and pressure of 20/40 samples of CARBOLITE for the nickel for being coated with different-thickness (psi) curve graph.

Figure 25 be 20/40 samples of CARBOLITE for being coated with nickel and copper conductivity (Siemens/m) in fixed closed pressure The curve graph of the time of fracturing fluid is exposed under power (psi).

Specific embodiment

In the following description, numerous specific details are set forth.It will be appreciated, however, that can these be specific thin Implement the embodiment of the present invention in the case of section.In other cases, well-known structure and technology are not shown specifically, in order to avoid Make the understanding to the description smudgy.

This document describes for detecting, position and be characterized in gas, make in the hydraulic fracturing of oil or geothermal reservoir stimulation Electromagnetism (EM) method of conductive supporting agent.Being sintered there is also described herein the conduction for being used as proppant in electromagnetic method, Substantially the particle of spheroidal and the slurry by salic raw material prepare this conductive sintering, substantially spheroidal The method of particle.As used herein, term " substantially spheroidal " and correlation form are defined as referring to minimum diameter and maximum is straight The mean ratio of diameter be about 0.8 or bigger or have compared with Krumbein and Sloss charts about 0.8 or bigger be averaged Sphericity value.

According to an embodiment of the invention, conductive particle (hereinafter referred to as " conductive supporting being sintered, substantially spheroidal Agent ") it can be made of conventional proppant, as the ceramic proppant, sand, resin that ceramic proppant, resin coat coat Husky, plastic bead and bead.These conventional proppants can be manufactured according to any suitable method, these methods are included but not It is limited to continuous spray atomization, spray-fluidized, spray drying or compression.United States Patent (USP) No.4,068,718,4,427,068,4, Suitable conventional proppants and its manufacturing method are disclosed in 440,866,5,188,175 and 7,036,591, in entire disclosure Appearance is incorporated herein by reference.

The performance (such as apparent specific gravity) of ceramic proppant changes since starting material is different with manufacturing method.It uses herein Term " apparent specific gravity " be per unit volume (gram/cc) particle weight, including interior porosity.Low-density supports Agent is typically below 3.0g/cm³Apparent specific gravity, and usually by kaolin and other aluminium oxide, oxide or silicate Ceramics are made.Medium density proppant usually has about 3.1 to 3.4g/cm³Apparent specific gravity, and usually by bauxite clay It is made.Proppant in high intensity is usually made of the bauxite clay with aluminium oxide, and with higher than 3.4g/cm³It is apparent Proportion.

Sintering, substantially spheroidal particle can be prepared by the slurry of salic raw material.In some embodiments In, alumina content of the particle with about 40% weight (wt%) to about 55wt%.In certain other embodiments, sintering , substantially spheroidal particle have about 41.5wt% to about 49wt% alumina content.

In certain embodiments, sintering, the substantially particle of spheroidal bulk density is about 1g/cm³, about 1.15g/ cm³, about 1.25g/cm³Or about 1.35g/cm³To about 1.55g/cm³, about 1.75g/cm³, about 2g/cm³Or about 2.5g/cm³.This Term " bulk density " used in text refers to the weight of per unit volume, and the volume including being considered, the hole between particle are empty Between.In certain other embodiments, particle has about 1.40g/cm³To about 1.50g/cm³Bulk density.

According to several exemplary embodiments, the substantially particle of spheroidal has any suitable according to ISO 13503- 5:The fluid of " Procedures for Measuring the Long-term Conductivity of Proppants " passes Conductance and permeability, and represented with darcy (Darcy) unit or darcy (D).These particles can have at least about 1D, at least About 2D, at least about 5D, at least about 10D, at least about 20D, at least about 40D, at least about 80D, at least about 120D or at least about 150D The prolonged permeation rate under 7500psi.These particles can have at least about 1D, at least about 2D, at least about 3D, at least about The prolonged permeation rate under 12000psi of 4D, at least about 5D, at least about 10D, at least about 25D or at least about 50D.These Grain can have at least about 100 millidarcies-foot (millidarcy-feet, niD-ft), at least about 200niD-ft, at least about 300niD-ft, at least about 500niD-ft, at least about 1000niD-ft, at least about 1500niD-ft, at least about 2000niD-ft, Or the long-term conductivity under 7500psi of at least about 2500mD-ft.For example, these particles can have at least about 50mD- Ft, at least about 100mD-ft, at least about 200mD-ft, at least about 300mD-ft, at least about 500mD-ft, at least about 1000mD- The long-term conductivity under 12000psi of ft or at least about 1500mD-ft.

In certain embodiments, sintering, substantially spheroidal particle have about 5% to about 8.5% Crushing strength and about 2500mD-ft under 10000psi to about 3000mD-ft the Long-term fluid conductivity under 10000psi. In some other embodiments, sintering, substantially spheroidal particle has about 5% to about 7.5% under 10000psi Crushing strength.

Sintering, substantially spheroidal particle can have any suitable apparent specific gravity.In one or more examples Property embodiment in, sintering, the substantially particle of spheroidal apparent specific gravity is less than 5, less than 4.5, less than 4.2, less than 4, it is small In 3.8, less than 3.5 or less than 3.2.In other embodiments, sintering, the substantially particle of spheroidal apparent specific gravity is About 2.50 to about 3.00, about 2.75 to about 3.25, about 2.8 to about 3.4, about 3.0 to about 3.5 or about 3.2 to about 3.8.This paper institutes Term " apparent specific gravity " (ASG) refers to the number of no unit, is defined as being numerically equal to body per cubic centimeter Product weight in gram, interstitial space or trepanning when being included in determining volume.

Sintering, substantially spheroidal particle can have any suitable size.According to one or more exemplary The particle of embodiment, substantially spheroidal can have at least about 100 mesh, at least about 80 mesh, at least about 60 mesh, at least about 50 Mesh or at least about size of 40 mesh.For example, substantially the particle of spheroidal can have about 115 mesh to about 2 mesh, about 100 mesh to about 3 mesh, about 80 mesh to about 5 mesh, about 80 mesh to about 10 mesh, about 60 mesh to about 12 mesh, about 50 mesh to about 14 mesh, about 40 mesh to about 16 The size of mesh or about 35 mesh to about 18 mesh.In a specific embodiment, the size of the substantially particle of spheroidal be about 20 to About 40 mesh (U.S.Mesh).

Suitable ceramic proppant can also be included according to vibration induced drippage (vibration-induced Dripping) method (is referred to herein as " drippage casting (drip casting) ") proppant of manufacture.Suitable drippage casting It makes method and proppant prepared therefrom is disclosed in United States Patent (USP) No.8,865,631 and No.8,883,693, U.S. Patent application public affairs No.2012/0227968 and U.S. Patent application No.14/502,483 and No.14/802,761 are opened, the entire disclosure is led to It crosses and is incorporated herein by reference.The proppant produced by drippage casting can have at least about 2.5, at least about 2.7, at least about 3, extremely Few about 3.3 or at least about 3.5 proportion.The proppant produced by drippage casting can have less than 5, is less than 4.5 or small In 4 proportion.Drippage casting proppant can also have less than 5 μm, less than 4 μm, less than 3 μm, less than 2.5 μm, less than 2 μm, Surface roughness less than 1.5 μm or less than 1 μm.In one or more exemplary embodiments, drippage casting proppant has Less than about 25 μm, less than about 20 μm, less than about 18 μm, less than about 16 μm, the average maximum less than about 14 μm or less than about 12 μm Aperture and/or less than 6 μm, less than 4 μm, less than 3 μm, less than 2.5 μm, less than 2 μm, the aperture less than 1.5 μm or less than 1 μm Standard deviation.In one or more exemplary embodiments, every square millimeter of proppant particles under the amplification factor of 500x In, drippage casting proppant has less than 5000, less than 4500, less than 4000, less than 3500, less than 3000, less than 2500 or Visible hole less than 2200.

There can be any suitable composition by the ceramic proppant for dripping casting or conventional method production.Ceramic support Agent can be or including any proper amount of silica and/or aluminium oxide.According to one or more embodiments, propped up based on ceramics Support agent total weight, ceramic proppant include less than 80wt%, less than 60wt%, less than 40wt%, less than 30wt%, be less than 20wt%, the silica less than 10wt% or less than 5wt%.According to one or more embodiments, ceramic proppant includes about 0.1wt% is to the silica of about 70wt%, about 1wt% to the silica of about 60wt%, about 2.5wt% to about 50wt%'s The silica or about 10wt% of silica, about 5wt% to about 40wt% to about 30wt% silica.According to one Or multiple embodiments, the total weight based on ceramic proppant, ceramic proppant include at least about 30wt%, at least about 50wt%, The aluminium oxide of at least about 60wt%, at least about 70wt%, at least about 80wt%, at least about 90wt% or at least about 95wt%.Root According to one or more embodiments, the alumina concentration of ceramic proppant is about 10wt%, about 20wt%, about 30wt% or about 40wt% to about 50wt%, about 60wt%, about 70wt%, about 80wt%, about 90wt% or about 95wt% or more.According to one A or multiple embodiments, ceramic proppant include about 30wt% to the aluminium oxide of about 99.9wt%, about 40wt% to about The aluminium oxide of 99wt%, about 50wt% are to the aluminium oxide of about 97wt%, the aluminium oxide of about 60wt% to about 95wt% or about The aluminium oxide of 70wt% to about 90wt%.In one or more embodiments, the ceramic support produced by method described herein Agent may include aluminium oxide, bauxite or kaolin or its any mixture.For example, ceramic proppant can be completely by aluminium oxide, aluminium Tu Kuang or kaolin or its any mixture form or substantially by aluminium oxide, bauxite or kaolin or its any mixture Composition.Term " kaolin " is it is well known in the art that and can include at calcined basis (calcined basis) On at least about alumina content of 40wt% and based on at least about raw material of the dioxide-containing silica of 40wt% on calcined basis.Art Language " bauxite " is it is known in the art that and can be or comprising at least about oxidation of 55wt% on calcined basis The raw material of aluminium content.As used herein, term " calcining " and correlation form refer to be enough to remove organic material and basic Processed raw material under the upper temperature and time for removing hydrate water.As used herein, term " not calcining " and correlation form Refer to the raw material of the naturally occurring volatile matter (for example, about 10 to about 40wt%) containing certain residual volume, which can To include organic material and chemically combined water (also referred to as " hydrate water ").

In any suitable stage in the manufacturing method of any one of these proppants, conduction material can be added in Material, such as, metal, conducting polymer, conductive carbon material (such as graphene) or conductive nano-particles are suitable for root to generate According to the proppant of the certain embodiments of the present invention.Conductive material can also be added to these proppants after proppant is manufactured Any one of in.Suitable metal includes aluminium, tin, zinc, iron, copper, silver, nickel, gold, platinum, palladium, rhodium etc., and can add in To generate the conductive supporting agent with any suitable tenor.Conductive supporting agent can have about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.5wt%, about 1wt%, about 2wt% or about 5wt% are to about 6wt%, about 8wt%, about The conductive metal concentration of 10wt%, about 12wt% or about 14wt%.

Suitable conducting polymer includes poly- (3,4- ethyldioxythiophenes) poly- (styrene sulfonate) (PEDOT： PSS), polyaniline (PANI), polypyrrole (PPY) etc., and can add in generate there is any Suitable conductive polymer to contain The conductive supporting agent of amount.Conductive supporting agent can have about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.5wt%, about 1wt%, about 2wt% or about 5wt% are to the conductive gold of about 6wt%, about 8wt%, about 10wt%, about 12wt% or about 14wt% Belong to concentration.

Suitable PEDOT：PSS, PANI and PYY conducting polymer can be commercially available from Sigma-Aldrich.Exist below Certain specific embodiments of the method with conductive polymer coated proppant are described in example 2.

Suitable conductive nano-particles include graphite, graphene, single wall or double-walled carbon nano-tube or with Nano Particle models Other materials of enough conductivity so as to detection are shown in the presence of enclosing in the present invention.Such electrical-conductive nanometer can be added in Grain has about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.5wt%, about 1wt%, about 2wt% or about to generate 5wt% to about 6wt%, about 8wt%, about 10wt%, about 12wt% or about 14wt% conductive nano-particles content.

Ceramic proppant can also be manufactured by way of generating porosity in proppant particles.Manufacture is suitable more The method of hole ceramic proppant is described in United States Patent (USP) No.7, and 036,591, the entire disclosure is incorporated herein by reference. In this case, conductive material can be impregnated into the hole of proppant particles, based on the total weight of conductive supporting agent, concentration It is about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.5wt%, about 1wt%, about 2wt% or about 5wt% are to about 6wt%, about 8wt%, about 10wt%, about 12wt%, about 15wt% or about 20wt%.Water soluble paint can be used (e.g., to gather Lactic acid) it is coated with these particles, to be allowed for the delay of conductive nano-particles that the different phase in fracture processing detects/fixed When discharge.

Ceramic proppant can have any suitable porosity.Ceramic proppant can have about 1%, about 2%, about 4%th, about 6%, about 8%, about 10%, about 12% or about 14% to about 18%, about 20%, about 22%, about 24%, about 26%, about 28%th, about 30%, about 34%, about 38%, about 45% or more internal interconnected pores rate.In several exemplary embodiments In, the inside interconnected pore rate of ceramic proppant is about 5% to about 35%, about 5% to about 15% or about 15% to about 35%. According to several exemplary embodiments, ceramic proppant can have any suitable average pore size.For example, ceramic proppant can be with With in its full-size about 2nm, about 10nm, about 15nm, about 55nm, about 110nm, about 520nm or about 1100 to about 2200nm, about 5500nm, about 11000nm, about 17000nm or about 25000nm or more average pore sizes.For example, ceramics branch Support agent can have in its full-size about 3nm to about 30000nm, about 30nm to about 18000nm, about 200nm to about The average pore size of 9000nm, about 350nm to about 4500nm or about 850nm to about 1800nm.According to certain implementations as described herein Example, sintering, substantially spheroidal particle be with made of continuous method, and in other embodiments, particle be with It has a rest made of method.

In one or more exemplary embodiments, conductive material can be added to ceramic proppant in its manufacturing method In.Referring now to Figure 1, it shows to prepare example be sintered, the substantially continuation method of the particle of spheroidal from slurry Sexual system.Exemplary system shown in FIG. 1 can have and the structurally and operationally class described in United States Patent (USP) No.4,440,866 As structurally and operationally, the complete disclosure of the patent is incorporated herein by reference.Exemplary system as shown in Figure 1 performs Operation can be used for preparing particle according to batch process, described in following article example 1.

In system shown in Fig. 1, ceramic raw material passes through pulverizer 105, and pulverizer 105 is by feed stock chip and is separated into Fritter.Ceramic raw material can have any suitable alumina content.For example, ceramic raw material can have about 10wt%, about 20wt%, about 30wt% or about 40wt% are to about 50wt%, about 60wt%, about 70wt%, about 80wt%, about 90wt% or about The alumina concentration of 95wt% or more.In some embodiments, when the raw material exploited or received (is herein referred as " untreated " Raw material) when there is such consistency (consistency) it is processed as described herein without fragmentation, it can be with Around pulverizer.The raw material supplied across pulverizer (such as shown in Fig. 1) is referred to as " processed " raw material.

In certain embodiments, salic raw material is separated into fritter and is sliced by pulverizer, small so as to obtain diameter In about 5 inches of small pieces, but the block with smaller and larger diameter can be further processed into slurry as described herein.Powder Broken machine and many other devices for being sliced, shredding or crushing salic raw material and the commercial source (example for it Such as Gleason Foundry Company) it is well known to those of ordinary skill in the art.

The blunger (blunger) 110 that processed or untreated salic raw material and water can be fed to, institute Stating blunger has the rotating blade for assigning its shearing force and further reduces the particle size of raw material to form slurry.Continuous In method, raw material and water are continuously fed into blunger.For manufacturing the blunger of the slurry of this material and similar dress It puts and is well known to those of ordinary skill in the art for its commercial source.

In certain embodiments, conductive material is added in salic raw material and the water in blunger 110, from And lead to conductive material a concentration of about 0.1wt% to about 10.0wt% or about 5.0wt% to about 10.0wt%, based on solid in slurry Body content or just before particle as described below is formed.

The water of sufficient amount can be added in blunger 110, to generate solid content in about 40 weight wt to about 60% model Enclose interior slurry.In certain embodiments, the water of sufficient amount is added in slurry so that the solid content of slurry is about 45wt% to about 55wt%.In other other embodiment, the water of sufficient amount is added in slurry so that the solid of slurry contains Amount is about 50wt%.The water for being added to blunger 110 can be fresh water or deionized water.In the continuation method for preparing slurry, The solid content of periodic analysis slurry, and the amount for being fed to the water in slurry is adjusted, to keep desired solid content.For The solid content for analyzing slurry and the method for the charging for adjusting water are well known to those of ordinary skill in the art and understand.

In certain embodiments, dispersant is added in the slurry in blunger 110, by the viscosity-adjusting agent of slurry extremely Target zone, as further discussed below.In other embodiments, reagent is adjusted by blunger by adding dispersant and pH The viscosity-adjusting agent of slurry in 110 is to target zone.

Dispersant can be added in slurry before addition conductive material or other additives.In some embodiments In, based on the dry weight of salic raw material, composition includes the dispersant of about 0.15wt% to about 0.30wt%.

The exemplary materials for being used as dispersant in composition as described herein and method is suitble to include but not limited to poly- third Olefin(e) acid sodium, ammonium polyacrylate, ammonium polymethacrylate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, polyphosphate, ammonium polyphosphate, lemon Sour ammonium, ferric citrate and polyelectrolyte (for example, composition of ammonium polymethacrylate and water), are purchased from various sources, Such as bought with trade name C-211 from Kemira Chemicals, with trade name BCS 4020 from Phoenix Chemicals, Bulk Chemical Systems are bought, and are bought with trade name DARVAN C from R.T.Vanderbilt Company, Inc.. In general, dispersant can the viscosity-adjusting agent of slurry to target viscosities so that slurry then across one of Fluidizer Or multiple drive nozzles carry out processed any material.In certain embodiments, target viscosities (are having less than 150 centipoises (cps) Have and measured on the Brookfield viscosimeters of #61 rotors).In other embodiments, target viscosities are less than 100cps.

According to the embodiment for wherein using pH adjusting agent, the pH adjusting agent of sufficient amount is added in slurry, by slurry PH adjust to about 8 to about 11 range.In certain embodiments, the pH adjusting agent of sufficient amount is added in slurry, it will PH is adjusted to about 9, about 9.5, about 10 or about 10.5.Can be by the pH of pH meter periodic analysis slurry, and charging can be adjusted The amount of pH adjusting agent into slurry is to maintain desired pH.For analyzing the charging of the pH of slurry and adjusting pH adjusting agent Method is in the limit of power of those of ordinary skill in the art.It is suitble to be used as pH adjustings in composition as described herein and method The exemplary materials of agent include but not limited to ammonia and sodium carbonate.

In general, the target viscosities of composition are can to pass through the drive nozzle processing of given type and size in Fluidizer Without the viscosity for becoming to block.In general, the viscosity of slurry is lower, given Fluidizer processing is more easily propagated through.However, add Adding excessive dispersant that the viscosity of slurry may be caused to increase to it satisfactorily cannot be passed through given Fluidizer to process Degree.Those of ordinary skill in the art can determine the target viscosities for giving Fluidizer type by routine experiment.

Blunger 110 mixes salic raw material, conductive material, water, dispersant and pH adjusting agent, until forming slurry Material.Formed slurry needed for time span depend on Multiple factors, such as the size of blunger, operate blunger speed and The amount of material in blunger.

From blunger 110, slurry is fed to tank 115, slurry is continuously agitated in tank 115, and oxygen-containing to be based on Change the amount addition adhesive of the gross dry weight about 0.2wt% to about 5.0wt% of aluminum feedstock and conductive material.In certain embodiments, Gross dry weight based on salic raw material and conductive material adds adhesive with the amount of about 0.2wt% to about 3.0wt%.It closes Suitable adhesive includes but not limited to polyvinyl acetate, polyvinyl alcohol (PVA), methylcellulose, dextrin and molasses.Certain In embodiment, adhesive is that molecular weight is from about 20000Mn to the PVA of about 100000Mn." Mn " represents number-average molecular weight, is In sample in the total weight of polymer molecule divided by the sample polymer molecule sum.

Tank 115 preserves the slurry generated by blunger 110.However, tank 115 can by the stirring less than blunger come Slurry is stirred, so that binding agent is made to be mixed with slurry, can extremely be hindered without the excessive foaming for causing slurry or the viscosity for increasing slurry The degree for hindering slurry that the pressurized nozzles of Fluidizer is passed through to feed.

In another embodiment, adhesive can be added to when in blunger in slurry.In such embodiment, Blunger optionally has variable speed, the height including being used to implement the high intensity that raw material is made to be broken into slurry form mixing Speed and for adhesive to be made to mix with slurry without causing above-mentioned excessive foaming or the increased low speed of viscosity.

Referring again to the tank 115 shown in Fig. 1, after adhesive is added in, the slurry sufficiently long time is stirred in tank So that adhesive is sufficiently mixed with slurry.In certain embodiments, after adhesive is added in, in tank by slurry agitation at most About 30 minutes.In other embodiments, slurry is stirred in tank 115 at least about 30 minutes.In yet another embodiment, adding After entering adhesive, stirring slurry is greater than about 30 minutes in tank.

Tank 115 can also be by one, two, three, or more the can system that forms of tank.It can make adhesive and slurry Expect that the tank of well-mixed any construction or quantity is enough.In a continuous process, can by from subsequent Fluidizer or One or more and water in the particle of the dust of other devices, oversize particles or undersize is added in tank 115 In slurry.

From tank 115, slurry is fed to heat exchanger 120, slurry is heated to about 25 DEG C to about 90 by heat exchanger 120 DEG C temperature.From heat exchanger 120, slurry is fed to pumping system 125, and slurry is fed to stream by pumping system 125 under stress Change device 130.

Grinder and/or screening system (not shown) may be inserted into the system shown in figure 1 by slurry be sent into flow Change one or more positions before device, the salic raw material by any large-size to be contributed to be crushed to suitable for charging To the target size of Fluidizer.In certain embodiments, target size is less than 230 mesh.In other embodiments, target size is small In 325 mesh, less than 270 mesh, less than 200 mesh or less than 170 mesh.Target size is by the drive nozzle in subsequent Fluidizer Type and/or size so that slurry atomization without the ability of blocking influence.

If using grinding system, filled with abrasive media, which is suitable for assisting raw material being crushed to suitable In the target size then fed by one or more drive nozzles of Fluidizer.If using screening system, sieve is designed Subsystem is more than the particle of target size to be removed from slurry.For example, screening system can include one or more sieves, these Sieve is chosen and is placed so that slurry is sieved into the particle less than target size.

Referring again to FIGS. 1, Fluidizer 130 has conventional design, such as in United States Patent (USP) No.3,533,829 and Britain it is special Described in sharp No.1,401,303.Comprising at least one atomizer 132 (three mists are shown in FIG. 1 in Fluidizer 130 Change nozzle 132), it is the drive nozzle with conventional design.In other embodiments, one or more two-fluid spray nozzles are to close Suitable.The design of this nozzle is well known, such as from K.Masters:" Spray Drying Handbook ", John Know in Wiley and Sons, New York (1979).

Also comprising grain bed 134, grain bed 134 can be supported Fluidizer 130 by plate 136, such as porous, straight or fixed To plate.Hot-air flows through plate 136.Grain bed 134 includes seed, and the green pellets with target size can be grown from seed (green pellets).As used herein, term " green pellets " and correlation form refer to be formed by slurry but unsintered base The particle of spheroidal in sheet.When using porous plate or straight panel, seed is additionally operable to obtain piston flow in Fluidizer.Piston flow is Term known to persons of ordinary skill in the art, and can be described generally as that the flowing mould that considerably less back mixing is closed wherein occurs Formula.Seed grain is less than the target size of green pellets prepared according to the methods of the invention.In certain embodiments, seed is accounted for by it About the 5% to about 20% of the total volume of the green pellets of formation.Under stress, slurry, and slurry are sprayed by atomizer 132 Seed is sprayed to form the green pellets of substantially spheroidal.

Before the atomization of slurry is started by Fluidizer, external seed can be placed on porous plate 136.If using outer Portion's seed can then prepare seed in similar to slurry technique shown in FIG. 1, and wherein seed is simply with target seed sizes It is taken out from Fluidizer.External seed can also be made in high intensity hybrid technique, for example, United States Patent (USP) No.4,879,181 Described in, the entire disclosure is incorporated herein by reference.

According to some embodiments, external seed is by having the alumina content at least identical with being used to prepare the raw material of slurry Raw material be made or be made by having than being used to prepare the raw material of the much the same aluminium oxide of the raw material of slurry.In certain implementations In example, the alumina content fewer than the alumina content of seed at least 10%, at least 20% or at least 30% of slurry.Other In embodiment, the alumina content of external seed is less than the alumina content of slurry, for example, than slurry alumina content as little as Few 10%, at least 20% or at least 30%.

Alternatively, the seed for grain bed is formed by the atomization of slurry, so as to provide seed " oneself of the slurry with its own The method of germination ".According to such an embodiment, in the case of the grain bed 134 there is no inoculation, across Fluidizer 130 Feed slurry.Leave the slurry droplet solidification of nozzle 132, but it is initial when it is sufficiently small so that they are by air stream from fluidisation It is taken out of in device 130 and captured by dust arrester 145 as " dust " (fine grained), dust arrester 145 can be for example, electrostatic removes Dirt device, cyclone separator, bag filter, wet scrubber or combination.Then the dust obtained from dust arrester is passed through into powder Dirt entrance 162 is fed to grain bed 134, is sprayed together with the slurry discharged from nozzle 132 in dust inlet 162.Dust can To recycle enough numbers, until them, to have grown into them too big and cannot be carried by air stream and can be used as seed Degree.Dust can also be recycled to during another operation, such as tank 115.

Referring again to FIGS. 1, hot-air is introduced by way of fan and air heater in Fluidizer 130,138 Place is schematically shown.Across grain bed 134 hot-air speed can be from about 0.9 meter per second to about 1.5 meter per seconds, and The depth of grain bed 134 is from about 2 centimetres to about 60 centimetre.When being introduced into Fluidizer 130, the temperature of hot-air is from about 250 DEG C to about 650 DEG C.Temperature when hot-air leaves Fluidizer 130 can be less than about 250 DEG C, and be less than in certain embodiments About 100 DEG C.

Optimize the distance between atomizer 132 and plate 136, to avoid dust formation (when nozzle 132 from plate 126 too Form dust when remote) and irregular coarse grained formed (irregular thick is formed when nozzle 132 is too near from plate 126 Grain).Analysis based on the powder sampled from Fluidizer 130 adjusts position of the nozzle 132 relative to plate 136.

The green pellets formed by Fluidizer is accumulated in grain bed 134.In a continuous process, as to Fluidizer 130 The green pellets formed by Fluidizer 130 is taken out in the reaction that Product Level in middle grain bed 134 is made across outlet 140, with Just given depth is kept in grain bed.The green pellets taken out from Fluidizer 130 is transmitted to elevator 155 by rotary valve 150, Green pellets is fed to screening system 160 by elevator 155, and green pellets is separated into one or more grades in screening system 160 Point, such as the fraction of oversized dimensions, product fraction and the fraction for crossing small size.

The fraction for leaving the oversized dimensions of sieve unit 160 includes being more than those green pellets of desired product size. In a continuous process, the green pellets of oversized dimensions can be recycled to tank 115, at least some excessive green pellets in tank 115 It can be decomposed and be mixed with the slurry in tank.Alternatively, the green pellets of oversized dimensions can be decomposed and be recycled to Fluidizer 130 In grain bed 134 in.The fraction for leaving the mistake small size of screening system 160 includes those less than desired product size Green pellets.In a continuous process, these green pellets can be recycled to Fluidizer 130, they can make in Fluidizer 130 Entrance 162 is passed through to be fed to Fluidizer 130 for seed or as two level charging.

The Product-level point for leaving screening system 160 includes those green pellets with desired product size.These lifes Pelletizing, which is sent to, to be pre-sintered in device 165 (for example, calcining furnace), and green pellets is done before sintering in device 165 is pre-sintered Dry or calcining.In certain embodiments, green pellets is dried to moisture less than about 18wt% or less than about 15wt%, small In about 12wt%, less than about 10wt%, less than about 5wt% or less than about 1wt%.

After drying and/or calcining, green pellets is fed in sintering equipment 170, the green pellets in sintering equipment 170 It is being enough to allow to burning of the recycling with one or more of desired apparent specific gravity, bulk density and crushing strength Particle tie, substantially spheroidal.If alternatively, sintering equipment 170 can provide before enough sintering conditions are carried out Enough calcinings and/or drying condition (that is, before sintering by the drying time of green pellets drying to target water content and temperature), It can then eliminate and be pre-sintered device 165.

The initial component of sintered particles and desired density are depended on for the specific time of sintering and temperature.At some In embodiment, sintering equipment 170 is the rotation that about 5 to about 90 minutes are operated at a temperature of about 1000 DEG C to about 1600 DEG C Kiln.In certain embodiments, temperature of the rotary kiln at about 1000 DEG C, about 1200 DEG C, about 1300 DEG C, about 1400 DEG C or about 1500 DEG C Degree is lower to be operated.In certain embodiments, residence time of the green pellets in sintering equipment is about 50 minutes to about 70 minutes or about 30 minutes to about 45 minutes.After particle leaves sintering equipment 170, size can be further screened, and be used for The test of quality control purpose.The oxidation conductive material is restricted or prevented can be sintered using inert atmosphere.With inert gas, For example, argon gas, nitrogen or helium, the technology instead of the oxygen-enriched atmosphere in sintering equipment is that those of ordinary skill in the art institute is ripe Know.In general, replace oxygen with inert gas so that retain 0.005% oxygen or less oxygen in sintering atmosphere.

Some embodiments according to the present invention, conductive material is coated on proppant.For example, it is left in proppant particles After sintering equipment 170, conductive material can be coated on ceramic proppant, and further screen size, be used in combination In the test of quality control method.Coating can be realized by any paint-on technique well known within the skill of those ordinarily skilled, Such as spraying, sputtering, vacuum deposition, dip-coating, extrusion, calendering, powder coating, print-on coating, airblade coating, roller coating, electroless plating Cover (for example, United States Patent (USP) No.3,296,012, No.4,812,202 and No.3, disclosed in 617,343, in entire disclosure Appearance be incorporated herein by reference), plating and brush.

According to several exemplary embodiments, conductive material is deposited on as coating on ceramic proppant or natural sand.Electricity Solution and the method for electroless are well known to those of ordinary skill in the art.For example, with reference to United States Patent (USP) No.3,556,839, Entire contents are incorporated herein by reference.

According to several exemplary embodiments, and according to conventional autocatalysis coating method, non-conductive substrate, example Such as, ceramic proppant sample is properly cleaned and is roughened, then by being continuously immersed in aqueous solution and the catalysis of reducing agent It is sensitized and activates in the aqueous solution of metal (for example, stannous chloride and palladium bichloride), and rinsed in water after each dipping.So Afterwards, base material is immersed in and be heated in 55 DEG C -95 DEG C of plating bath.In the presence of (for example, sodium citrate and sodium acetate etc.) salt, The bath can include for example, the aqueous solution containing nickel salt and phosphorous reducing agent (such as sodium hypophosphite), the pH of wherein solution adjust to Value is between 4 and 6.It will be appreciated by the skilled addressee that any conventional electroless nickel plating, copper, silver or gold plating can be used Bathe solution, such as those commercially available from the supplier of such as Uyemura, Transene or Caswell.Dipping about 1 to about 30 Minute time can generate deposition thickness on the surface of the substrate be about 0.05 micron, about 0.1 micron, about 0.25 micron, Or about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or about 5 microns or thicker of nickel film.Plating solution can continuously again For the plating chemical concentrations giving to keep constant or on the contrary, plating solution is on base material and basic as plating reagent is deposited on It exhausts, so as to which the thickness for making metal film is fixed.

According to several exemplary embodiments, and according to conventional electroless process, non-conductive substrate is suitably cleaned, For example, ceramic proppant sample, then by be continuously immersed in catalytic metal aqueous solution and reducing agent aqueous solution (for example, chlorine Change the solution of palladium and stannous chloride) in be sensitized, and rinsed in water after such dipping every time.Hereafter, base material is immersed into temperature Degree is maintained in the plating bath between 25-65 DEG C.In the presence of one or more salt (for example, sodium potassium tartrate tetrahydrate and sodium carbonate), The bath can include for example, the aqueous solution containing mantoquita and alkali metal hydroxide salt.It will be appreciated by the skilled addressee that Can use any conventional electroless nickel plating, copper, silver or golden plating bath solution, for example, can from such as Uyemura, Transene or Those solution commercially available from the supplier of Caswell.Dipping can generate the thickness of deposition on the surface of the substrate for about 1 to about 30 minute Degree is about 0.05 micron, about 0.1 micron, about 0.25 micron or about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or about 5 microns or thicker of nickel film.Plating solution can continuously again for give the plating chemical concentrations kept constant or on the contrary, Plating solution is exhausted substantially as plating reagent is deposited on base material, so as to which the thickness for making metal film is fixed.

However, conventional autocatalysis coating method can use acid palladium solution, acid palladium solution is oxidable natural The active metal of (expressed) is showed in proppant surface, therefore bad deposition of the metal in proppant surface can be caused. It has been found that regulating step, which is attached in no electrocoating method, can improve deposition of the metal in proppant surface.

Referring now to Figure 2, describing flow chart, conductive material is layed onto support without electropaining it illustrates regulating step is used The step of technique 200 in agent.In no electrocoating method 200, one is directed by the proppant supply of pipeline 202 In a or multiple washing units 204, wherein the proppant via pipeline 202 can contact to remove dust with the first washing solution And/or fine powder by pipeline 206 to provide clean proppant.Washing unit 204 can be or including one or more tanks, one A or multiple containers, one or more transport systems, one or more pipelines etc..First, which washs solution, can be or including containing The aqueous solution of acid or alkali, for example, water or organic phase solution (for example, liquid hydrocarbon) containing diluted acid, the washing can also increase At a temperature of carry out.It can be discharged from washing unit 204 by the cleaning proppant of pipeline 206 and be introduced in one or more A pretreatment unit 208, wherein the cleaning proppant by pipeline 206 can be contacted with adjusting solution.Pretreatment unit 208 can To be or including one or more tanks, one or more containers, one or more transport system, one or more conduits etc.. Adjusting solution can be or including alkaline solution, the pH of proppant surface is adjusted to alkaline level (pH>7).Alkaline solution It can include one or more in hydroxide, ammonia or carbonate.

By combining or mixing suitable surfactant with adjusting solution, can further enhance in pretreatment unit Adjusting in 208.Suitable surfactant may include but be not limited to anion, cation, nonionic and amophoteric surface active Agent or combination.According to several exemplary embodiments, suitable surfactant is including but not limited to saturated or unsaturated Long chain fatty acids or hydrochlorate, long-chain alcohol, polyalcohol, polysorbate, dimethyl polysiloxane and polyethylene hydrogen siloxane.According to Several exemplary embodiments, suitable surfactant include but not limited to straight chain and branch with about 4 to about 30 carbon atoms Chain carboxylic acid and hydrochlorate have the straight chain of about 4 to about 30 carbon atoms and branched alkyl sulfonic acids and hydrochlorate, wherein linear alkyl chain packet Include the linear alkylbenzene sulfonate (LAS) of about 4 to about 30 carbon atoms, sulfosuccinate, phosphate, phosphonate, phosphatide, ethyoxyl Change compound, carboxylate, sulfonate and sulfate, polyglycol ether, amine, the salt of acrylic acid, pyrophosphate and its mixture. In one or more illustrative embodiments, surfactant is polysorbate, such as Tween^TM20 (PEG (20) dehydrations Sorbitan monolaurate).

By the cleaning proppant of pipeline 206 can under any suitable conditions of with the adjusting in pretreatment unit 208 Solution contacts, to provide proppant after the adjustment by pipeline 210.Suitable condition can include about 10 DEG C, about 25 DEG C, about 30 DEG C, about 35 DEG C, about 40 DEG C, about 45 DEG C to about 47 DEG C, about 50 DEG C, about 55 DEG C, about 60 DEG C, the temperature of about 75 DEG C or about 100 DEG C, At about 1 second, about 5 seconds, about 15 seconds, about 25 seconds, about 45 seconds or about 55 seconds to about 65 seconds, about 75 seconds, about 100 seconds, about 2 minutes (min), under the residence time of about 5 minutes or about 10 minutes.Adjust solution can have at least about 7.2, at least about 8, at least about 8.5th, at least about 9, at least about 10, at least about 11, at least about 12, at least about 12.5 or at least about 13 pH.

It can be taken out from pretreatment unit 208 by the proppant after the adjustment of pipeline 210 and introduce one or more Haze reduction unit 212, can be molten with the second washing by the proppant after the adjustment of pipeline 210 in haze reduction unit 212 Liquid contacts, with the washing proppant for further removing dust and/or particulate to provide via pipeline 214, and via pipeline 210 Proppant after the adjustment is compared with the turbidity reduced.Haze reduction unit 212 can be or including one or more tanks, one Or multiple containers, one or more transport systems, one or more pipelines etc..Second washing solution can be with the first washing solution It is same or like, and aqueous solution (for example, water) or organic phase solution (for example, liquid hydrocarbon) can be included.Second washing solution There can also be the sensitizer of the coactivator in subsequent step.Sensitizer can be any reagent of reduction activator, example Such as, stannic chloride, sodium borohydride or sodium hypophosphite or any other known reducing agent.In one or more exemplary embodiments In, the second washing solution is free of sensitizer.To be another rinsing step after sensitizer step, but in some embodiments Sensitizer step can be omitted.

It can be discharged by the washed proppant of pipeline 214 from haze reduction unit 212 and introduce one or more Catalyst reduction unit 216, wherein the proppant for the washing for passing through pipeline 214 can be contacted with activated solution.Activated solution can To activate proppant by the way that catalytically-active materials (for example, palladium, silver or iron) are attached to proppant surface.Activated solution can To be or including one or more palladium salts, for example, palladium bichloride or ammonium chloropalladate (palladium ammonium chloride) And/or silver nitrate.Activated solution can be aqueous phase solution or organic phase solution.Activated solution can have about every liter 0.1mg Pd²⁺(mg/l), about 0.5mg/l, about 1mg/l, about 5mg/l, about 10mg/l or about 20mg/l are to about 30mg/l, about 35mg/l, about The palladium salt concentration of 40mg/l, about 50mg/l or about 100mg/l.Activated solution can also contain reducing agent or sensitizer.Reducing agent Can be or comprising pink salt, for example, stannous chloride.In one or more exemplary embodiments, activated solution is free of reducing agent.

By the washed proppant of pipeline 214 can under any suitable conditions of with catalyst reduction unit 216 In activated solution contact, to provide activated proppant by pipeline 218.Suitable condition can include about 20 DEG C, about 35 DEG C, about 50 DEG C, about 65 DEG C, about 75 DEG C, about 78 DEG C to about 82 DEG C, about 85 DEG C, about 90 DEG C, about 95 DEG C, about 100 DEG C or about 105 DEG C temperature, at about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes or about 7 minutes to about 8 minutes, about 9 points Clock, about 10 minutes, about 12 minutes, about 15 minutes or about 20 minutes are longer and/or when bath foam substantially used up stop Between.Activated solution can have about 7.1, about 7.2, about 7.4, about 7.6 or about 7.8 to about 8, about 8.5, about 9, about 9.5, about 10, About 11, the about 12 or about 13 or pH of bigger.

It can be discharged by the activated proppant of pipeline 218 from activation unit 216 and be introduced into one or more punchings Unit 220 is washed, is contacted wherein by the activated proppant of pipeline 218 solution can be washed with third, with from activated branch Excessive activated solution is removed in support agent.Rinsing unit 220 can be or including one or more tanks, one or more container, One or more transport systems, one or more pipelines etc..Third washing solution can include aqueous solution, for example, tap water or Deionized water.

It can be discharged by the proppant through flushing of pipeline 222 from rinsing unit 220 and be introduced in one more In metallization ceH 242, wherein the proppant through flushing by pipeline 222 can be subjected to metal deposition.Show in one or more In example property embodiment, it can be passed through in any suitable manner by contacting plating solution by the proppant through flushing of pipeline 222 By metal deposition.Plating solution can be sprayed or be coated to the branch through flushing on the proppant through flushing and/or passing through pipeline 222 Support agent can be dipped into or be immersed in plating bath of liquid (plating bath solution).For example, in metallization ceH 224, pass through pipeline 222 Proppant through flushing can immerse temperature be about 20 DEG C, about 35 DEG C, about 50 DEG C, about 60 DEG C or about 70 DEG C to about 75 DEG C, about 80 DEG C, about 90 DEG C, about 95 DEG C, about 100 DEG C, in about 110 DEG C or about 120 DEG C or higher plating bath solution, the residence time is about 1 point Clock, about 2 minutes, about 4 minutes, about 8 minutes, about 12 minutes or about 14 minutes to about 16 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 45 minutes or about 60 minutes or for more time and/or substantially used up until bathing.After immersion, conductive material The range of film is from about 10 nanometers (nm), about 50nm, about 100nm, about 250nm or about 400nm to about 500nm, about 600nm, about 700nm, about 800nm, about 900nm, about 1,000nm, about 1,200nm, about 1,500nm, about 2,000nm or about 3,000nm or more Greatly, it can essentially homogeneously be coated on the proppant through flushing to provide conductive supporting agent.

Plating solution can be the aqueous solution containing water or the organic phase solution containing one or more hydrocarbon.Plating solution can be alkalinity Or acid, and metal salt, complexing agent, reducing agent and buffer can be included.For example, plating solution can include nickel salt, example Such as, nickel sulfate, nickel sulfate hexahydrate close object and nickel chloride.Complexing agent can include acetate, succinate, Glycinates, third Diacid salt, pyrophosphate, malate or citrate, or any combination thereof.Reducing agent can include sodium borohydride, diformazan Amine borine or hydrazine, or any combination thereof.Buffer solution can include acetic acid, propionic acid, glutaric acid, succinic acid or adipic acid or its What is combined.It will be appreciated by the skilled addressee that any conventional electroless nickel plating, copper, silver or golden plating solution can also be used, Such as those commercially available from the supplier of such as Uyemura, Transene, Caswell and Metal-Chem.

Additional and/or alternative steps can be used in electroless plating.Referring now to Fig. 3, flow chart is shown, show The step of having gone out for conductive material to be layed onto to technique 300 on proppant without electropaining, wherein depicting activation and the gold of replacement Belong to deposition step.Proppant particles can carry out alkalinity and adjust 301, can adjust phase with the alkalinity in pretreatment unit 208 It is same or similar, to provide proppant particles after the adjustment.

After alkaline regulating step 301 is carried out, proppant particles after the adjustment can be before electroless metal deposition 303 Carry out activation step 302.Particle after the adjustment is made to be sensitized generating through sensitization using the sensitizer solution of tin (II) 304 Grain.It is subsequently exposed in palladium (II) activated solution 305, palladium (II) is reduced into palladium metal (Pd on the particle surface through sensitization²⁺ →Pd⁰), tin (II) is oxidized to tin (IV) (Sn²⁺→SN⁴⁺).After palladium (II) activated solution 305 is exposed to and without electric gold Before belonging to deposition 303, accelerator solution 306 can be used for the tin (IV) except deoxidation.Alternative embodiment is related to the tin of combination (IV) and palladium (II)) activator and sensitizer suspension 307, be followed by accelerator solution 306.Accelerator solution 306 can be Aqueous solution, and one or more accelerating agents can be included, including but not limited to one or more organic sulfur compounds, such as poly- two Two propane sulfonic acid sodium of sulphur (bis (sodium-sulfopropyl) disulfide), 3- sulfydryl -1- propane sulfonic acid sodium salt, N, N- diformazans Base-Dithiocarbamyl propane sulfonic acid sodium salt or 3-S- isothiourea propane sulfonic acid salt and its mixture.Other suitable accelerating agents It can include but is not limited to thiocarbamide, allylthiourea, acetyl thiourea and pyridine etc..

In certain embodiments, proppant particles surface is specific to, alkalinity is adjusted and/or the combination of solution drying can be only It is activated using Pd activators, as depicted in step 308.It uses any suitable palladium salt (for example, palladium bichloride or ammonium chloropalladate) Activate particle after the adjustment, a concentration of every liter about 0.1mg, about 0.5mg, about 1mg, about 5mg, about 10mg, about 15mg or About 20mg to about 25mg, about 30mg, about 35mg, about 40mg or about 50mg or more milligrams Pd²⁺, can use any suitable Alkali (for example, sodium hydroxide or ammonia) adjusts the pH of solution between 7 and 14.

In one or more exemplary embodiments, intrinsic surface active 309 can be before electroless metal deposition 303 It completes.In this embodiment, iron or during calcining or sintering mix proppant particles in any other suitable metal from Son shows (expressed) on the surface of proppant, can be directly used for activated particle.In one or more exemplary embodiments In, the surface of particle by particle by immersing reducing agent solution (for example, sodium borohydride, sodium hypophosphite or sodium cyanoborohydride) In activate, wherein the solution can be transferred directly in electroless plating liquid, wherein particle is still soaked from solution or this is molten Liquid is dried on particle or completely from particle before electroless plated metal 303 and rinses.

Ceramic proppant particle can contain a large amount of iron oxide.In one or more examples of intrinsic surface active 309 Property embodiment in, these iron fragments can be reduced into copper, nickel and other noble metal electroless plating liquid have catalytic activity element Iron or other reduction forms [iron (II)].It, can be in the feelings of no Pd activators by using the intrinsic natural iron content of particle It is plated on particle under condition.Surface Fe ion reduction can occur, such as sintering equipment 170 for atom iron in sintering equipment, Or after sintering, by keeping the reducing environment in kiln, it is characterised in that there are the products that carbon monoxide or other parts burn. Iron on proppant particles surface can also be after fabrication by sudden and violent by the surface of proppant particles at any suitable temperature It is exposed under carbon monoxide or hydrogen and is reduced, for example, about 200 DEG C, about 300 DEG C, about 400 DEG C, about 500 DEG C or about 600 DEG C extremely About 750 DEG C, about 900 DEG C, about 1100 DEG C or about 1500 DEG C.

After particle activation 302, activated proppant 310 can be converted into conductive branch by electroless metal deposition 303 Support agent 311.Method for being electrolysed with electroless is well known to those of ordinary skill in the art.It is special see, for example, the U.S. Sharp No.3,556,839, entire contents are incorporated herein by reference.According to several exemplary embodiments, and according to routine Autocatalysis or electroless method, activated proppant sample can by various methods be applied with metal and metal alloy It covers.

Activation 302 after, base material can be immersed, impregnated, sprayed or in other ways with electroless metal deposition 303 Plating solution contact, to provide conductive supporting agent 311.Plating solution can be heated to about 35 DEG C, about 45 DEG C, about 55 DEG C, about 65 DEG C or About 75 DEG C to about 85 DEG C, about 95 DEG C, about 105 DEG C or about 120 DEG C or higher temperature.In one or more embodiments, plating solution Can be or the acid including having high content of phosphorus (phosphorus of about 5wt% to about 12wt%, the weight based on gained nickel-phosphor alloy film) Property solution containing nickel 312.The solution of high content of phosphorus can include for example in the presence of salt (for example, sodium citrate and sodium acetate), contain There is the aqueous solution of nickel salt and phosphorous reducing agent (for example, sodium hypophosphite).The pH of high content of phosphorus plating solution can from about 2, about 3, about 3.5th, about 4 or about 4.5 to about 5, about 5.5, about 6 or about 6.5.

In one or more embodiments, plating solution can be with low phosphorus content (about>The phosphorus of 1wt% to about 4.9wt%, Weight based on gained nickel-phosphor alloy film) alkaline solution containing nickel 313.The pH of alkali plating solution 313 with low phosphorus content can be with From about 7, about 7.5, about 8, about 8.5 or about 9 to about 10, about 10.5, about 11, about 12 or about 13 or higher.Alkaline coating bath 313 can To chelate free nickel ion to prevent the solution reaction with Pd, as Pd solution drag-out (drag out) may occur Equally, therefore for high surface area material (for example, ceramic proppant) preferred reaction environment is provided.Alkali plating solution may need The relatively longer time carrys out plating, but can lead to thinner adjoining coating, has higher electric conductivity, this can enhance electricity Magnetic testi.It will be appreciated by the skilled addressee that any conventional electroless nickel plating, copper, silver or golden plating solution can be used, With any pH ranges, such as can be from the supply of such as Metal-Chem, Enthone, Uyemura, Transene or Caswell Those commercially available from quotient.In one or more exemplary embodiments, plating solution can be or including containing formaldehyde as reducing agent Alkaline electroless copper 314.In one or more exemplary embodiments, plating solution can include electroless plating noble metal 315, for example, Silver, gold and platinum.For example, plating solution can be or including silver nitrate solution.

Conductive supporting agent 311 can have the conductive material of any suitable film thickness degree of setting on its outer surface. In one or more embodiments, it is conductive when being substantially homogeneously coated on proppant to provide conductivity ceramics proppant 311 The film thickness of material can be about 10nm, about 50nm, about 100nm, about 250nm or about 400nm to about 500nm, about 600nm, about The thickness of 700nm, about 800nm, about 900nm, about 1000nm, about 1200nm, about 1500nm, about 2500nm or about 3500nm or bigger Degree.In one or more exemplary embodiments, the thickness of the substantially homogeneous coating of conductive material can be about 50nm to about 150nm, about 400nm are to about 600nm, about 500nm to about 1200nm, about 550nm to about 700nm, about 750nm to about 1200nm, Or about 750nm to about 1000nm.

Conductive material can also be attached in resin material.Ceramic proppant or natural sand can be with including conductive material (for example, metal cluster, sheet metal, metal ray, metal powder, metalloid, metal nanoparticle, quantum dot, carbon nanotube, bar This special fullerene (buckminsterfullerene) of Triprolidine Hydrochloride and other suitable conductive materials) resin material coat, to carry For the proppant containing conductive material that can be detected by calutron.It is that this field is general that resin, which coats proppant and the method for natural sand, Known to logical technical staff.Suitable solvent is described for example, the United States Patent (USP) No.3 of Graham et al., in 929,191 to apply Coating method, entire contents are incorporated herein by reference.United States Patent (USP) No.3,492,147 (its entire disclosure of Young et al. Content is incorporated herein by reference) described in another suitable method include with the uncatalyzed resin composition of liquid Grain base material, it is characterised in that it can extract catalyst or curing agent from non-aqueous solution.In addition, the United States Patent (USP) of Graham et al. No.4 describes the suitable hot melt painting method for using phenol-formaldehyde novolaRs resin, whole in 585,064 Disclosure is incorporated herein by reference.Those of ordinary skill in the art will be familiar with coating proppant and natural sand for resin Other suitable methods.

Conductive supporting agent 311 can have any suitable conductivity.It is conductive in one or more exemplary embodiments The filling layer (pack) 311 of proppant can have at least about 1 every meter of Siemens (S/m), at least about 5S/m, at least about 15S/m, At least about 50S/m, at least about 100S/m, at least about 250S/m, at least about 500S/m, at least about 750S/m, at least about 1000S/ M, at least about 1500S/m or at least about conductivity of 2000S/m.The conductivity of the filling layer 311 of conductive supporting agent may be About 10S/m, about 50S/m, about 100S/m, about 500S/m, about 1000S/m or about 1500S/m to about 2000S/m, about 3000S/m, About 4000S/m, about 5000S/m or about 6000S/m.The filling layer 311 of conductive supporting agent can have any suitable resistivity. In one or more exemplary embodiments, the filling layer 311 of conductive supporting agent can have less than 100Ohm-cm, be less than 80Ohm-cm, less than 50Ohm-cm, less than 25Ohm-cm, less than 15Ohm-cm, less than 5Ohm-cm, less than 2Ohm-cm, be less than 1Ohm-cm, the resistivity less than 0.5Ohm-cm or less than 0.1Ohm-cm.

In one or more exemplary embodiments, load or pressure on the filling layer 311 of conductive supporting agent increase by 2 Times, the conductivity increase at least about 50% of 5 times or 10 times filling layers 311 that can make conductive supporting agent, at least about 75%, extremely Few about 100%, at least about 150% or at least about 200%.In one or more exemplary embodiments, by conductive supporting agent Load or pressure on filling layer 311 increase by 2 times, the 5 times or 10 times resistivity that can make the filling layer 311 of conductive supporting agent Reduce about 1%, about 2% or about 5% to about 10%, about 15% or about 25%.

Turning now to Fig. 4, ceramic raw material passes through pulverizer 105 and feeds to blunger 110, is mixed in blunger 110 Ceramic raw material, water, dispersant, and/or pH adjusting agent are until form slurry.Slurry is fed from blunger 110 into tank 115, Slurry is continuously stirred in tank 115 and adds in adhesive.Slurry is fed to heat exchanger 120, heat exchanger 120 from tank 115 Slurry is heated to required temperature.Slurry is fed to pumping system 125 from heat exchanger 120, slurry is fed to by pumping system 125 Fluidizer 430.Fluidizer 430 can have any conventional design, as described herein.For example, Fluidizer 430 can be with fluidisation Device 130 is same or similar.Including at least one atomizer 132 (three atomizers can be shown in FIG. 4 in Fluidizer 430 132).Fluidizer 430 can also include activation nozzle 432 (two activation nozzles 432 are shown in Fig. 4), be also conventional set The nozzle of meter.Fluidizer 430 further includes the grain bed 134 that the plate 136 that can be flowed through by hot-air supports.Slurry leads under stress It crosses atomizer 132 to spray, and slurry spraying seed can use it to form the substantially green pellets of spheroidal and/or slurry The seed of itself germinates certainly.

The green pellets formed by Fluidizer 430 can be accumulated in grain bed 134.Activating nozzle 432 can be incited somebody to action by pipeline 434 To provide activated green pellets on the green pellets that activated solution is ejected into Fluidizer 430 and grain bed 134.Pass through pipeline 434 activated solution can be aqueous phase solution or organic phase solution.For example, the activated solution for passing through pipeline 434 can be or can To include any activated solution disclosed herein.In one or more exemplary embodiments, the activation by pipeline 434 is molten Liquid can include the metal of aluminium, tin, zinc, iron, copper, silver, nickel, gold, platinum, palladium, rhodium etc..In one or more exemplary implementations In example, by the activated solution of pipeline 434 can by by catalytically-active materials (for example, palladium or silver) be attached to green pellets surface come Activate green pellets.Activated solution by pipeline 434 can also be or can include one or more palladium salts, for example, palladium bichloride Or ammonium palladic chloride, and/or silver nitrate.0.1 milligram of Pd can be about by the palladium salt concentration of the activated solution of pipeline 434²⁺Every liter (mg/l), about 0.5mg/l, about 1mg/l, about 5mg/l, about 10mg/l or about 20mg/l are to about 30mg/l, about 35mg/l, about 40mg/l, about 50mg/l or about 100mg/l or bigger.Reducing agent or sensitization can also be contained by the activated solution of pipeline 434 Agent.Reducing agent can be or including pink salt, for example, stannous chloride.In one or more exemplary embodiments, pass through pipeline 434 activated solution does not include reducing agent.It, can by the activated solution of pipeline 434 in one or more exemplary embodiments To be or can include activated solution 305, accelerator solution 306, and/or activator and sensitizer suspension 307.At one or In multiple exemplary embodiments, activated solution can include palladium (II) (Pd2+), tin (IV) (Sn2+), elemental iron, and/or iron (II)。

In continuous processing, in response to the Product Level in the grain bed 134 in Fluidizer 430, taken out by outlet 140 The activated green pellets formed in Fluidizer 430, to keep given depth in grain bed.Rotary valve 150 will be from The activated green pellets that Fluidizer 430 takes out is guided to elevator 155, and activated green pellets is fed to by elevator 155 Screening system 160, activated green pellets is separated into one or more fractions in screening system 160, for example, oversized dimensions Fraction, product fraction and cross small size fraction.The fraction for leaving the oversized dimensions of sieve unit 160 includes being more than institute's phase Those activated green pellets of the product size of prestige.In continuous processing, the activated green pellets of oversized dimensions can be again Be recycled in tank 115, in tank 115 the activated green pellets of at least some oversized dimensions can be decomposed and with the slurry in tank Mixing.Alternatively, the activated green pellets of oversized dimensions can be decomposed and be recycled to the grain bed 134 in Fluidizer 430 In.The fraction for leaving the mistake small size of screening system 160 includes being less than those activated green-balls of desired product size Group.In continuous processing, these activated green pellets can be recycled in Fluidizer 430, in Fluidizer 430 they Seed can be used as or fed as two level and entrance 162 is passed through to be fed to Fluidizer 430.

The Product-level point for leaving screening system 160 includes those activated green-balls with desired product size Group.These activated green pellets, which are sent to, to be pre-sintered in device 165 (for example, calcining furnace), through work in device 165 is pre-sintered The green pellets of change is dried or is calcined before sintering.In certain embodiments, activated green pellets, which is dried to, is less than about 18wt% or the moisture less than about 15wt%, about 12wt%, about 10wt%, about 5wt% or about 1wt%, to provide warp Dry green pellets.

Dried green pellets can include (one or more) activated metal and/or (one or more) catalytic activity object Matter.For example, dried green pellets can include palladium, iron, silver etc..It is dried in one or more exemplary embodiments Green pellets can include palladium metal (Pd⁰), tin (IV) (Sn⁴⁺), iron oxide (II), iron oxide (II, III), and/or iron oxide (III).For example, when activated solution 305 includes palladium (II), palladium (II) is reduced to palladium metal (Pd on the surface of green pellets²⁺ →Pd⁰), and when activated solution 305 contains tin (II), tin (II) is oxidized to tin (IV) (Sn on green pellets surface²⁺→ Sn⁴⁺) when can assist reduction Pd.In one or more exemplary embodiments, about 1wt%, about 2wt%, about 4wt%, about 8wt%, about 15wt%, about 30wt% or about 40wt% are to about 60wt%, about 70wt%, about 80wt%, about 90wt%, about The catalytically-active materials of 95wt% or about 99wt% can show on the outer surface of the green pellets in calcining furnace.

After drying and/or calcining, green pellets is fed in sintering equipment 170, the green pellets in sintering equipment 170 It is being enough to allow to sintering of the recycling with one or more of desired apparent specific gravity, bulk density and crushing strength , period of the substantially particle of spheroidal is sintered.If alternatively, sintering equipment 170 can provide enough calcinings and/ Or drying condition and then can provide enough sintering conditions, then it can remove and be pre-sintered device 165.

After the pelletizing through sintering leaves sintering equipment 170, they can further be screened size, and be used for The test of quality control purpose.The amount of oxidation that can also be sintered to limit green pellets using inert atmosphere prevents catalytic activity The further oxidation of green pellets.The oxygen-enriched atmosphere in sintering equipment is replaced with inert gas (for example, argon gas, nitrogen or helium) Technology be well known to those of ordinary skill in the art.In general, oxygen can be replaced with inert gas so that in sintering atmosphere The middle oxygen for retaining 0.005% or less oxygen.

After the green pellets for generating catalytic activity, some embodiments according to the present invention will be led in plating unit 175 Electric material is coated on the pelletizing or proppant through sintering.For example, the pelletizing through sintering taken out from sintering equipment 170 or support Agent can be introduced in plating unit 175, and proppant is dipped into plating solution disclosed herein in plating unit 175, the plating Liquid may include the temperature between about 55 DEG C to 95 DEG C or between about 25 DEG C to 65 DEG C.Dipping about 1 minute to about 30 minutes when Between can to generate deposition thickness on substrate surface be about 0.05 micron, about 0.1 micron, about 0.25 micron or about 0.5 micron To about 1 micron, about 2 microns, about 3 microns or about 5 microns or thicker of nickel film.Plating solution can be continuously again for giving in plating The plating chemical concentrations that are kept constant in unit 175 or on the contrary, plating solution is deposited on plating reagent on base material and by base Originally it exhausts, so as to which the thickness for making metal film is fixed.Conductive supporting agent can be taken out by pipeline 180 from plating unit 175.

Turning now to Fig. 5 and Fig. 6, the slurry of ceramic raw material is formed in blunger 110, and is fed in tank 115, Slurry is continuously agitated and adds adhesive in tank 115.Slurry is fed to heat exchanger 120 from tank 115, is then fed To pumping system 125, slurry is fed to Fluidizer 130 to provide green pellets by pumping system 125.Then, it is taken out by outlet 140 The green pellets formed in Fluidizer 130.The green pellets taken out from outlet 140 then can be in any suitable manner in any conjunction The suitable time is contacted with activated solution disclosed herein, to provide activated green pellets before sintering.According to Fig. 5 System, leaving the green pellets of rotary valve 150 can contact in any suitable manner through the disclosed herein of pipeline 502 Activated solution.For example, it can be sprayed-on or otherwise be ejected by the activated solution of pipeline 502 to leave rotary valve 150 Green pellets on to provide activated green pellets.The liquid stream of activated solution can also be contacted by leaving the green pellets of rotary valve 150 Or bath of liquid is to provide activated green pellets.Activated green pellets is then directed into elevator 155.In one or more examples Property embodiment (not shown) in, when green pellets leaves elevator and/or when green pellets is when on screening system 160, activation is molten Liquid can be injected on green pellets to provide activated green pellets.Activated green pellets with product size is from screening Be removed and be sent in system 160 and be pre-sintered device 165 and/or sintering equipment 170, with provide oxidized green pellets and/ Or proppant.

According to the system of Fig. 6, leave the green pellets with product size of screening system 160 and can contact and pass through pipeline 602 activated solution.In one or more exemplary embodiments, the Product-level point for leaving screening system 160 includes having institute Those green pellets of desired product size.These green pellets can contact activated solution in any suitable manner.It is for example, logical Cross the activated solution of pipeline 602 can be sprayed or otherwise be sprayed on the green pellets with desired product size with Activated green pellets is provided.Green pellets with desired product size can also contact the liquid stream or bath of liquid of activated solution To provide activated green pellets.Activated green pellets is fed to and is pre-sintered device 165 and/or sintering equipment 170, to carry For oxidized green pellets and/or proppant.

Some embodiments according to the present invention, conductive material are applied to the proppant of the system production according to Fig. 5 and Fig. 6 On.For example, the pelletizing through sintering or proppant that take out from sintering equipment 170 be directed into plating unit 175 and It is dipped into the plating solution being arranged in plating unit 175, which can be included between about 55 DEG C -95 DEG C or about 25-65 DEG C Between temperature.Dipping time of about 1 to about 30 minute can generate the thickness of deposition on substrate surface be about 0.05 micron, About 0.1 micron, about 0.25 micron, about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or about 5 microns or thicker of nickel Film.Plating solution can continuously again for give the plating chemical concentrations kept constant or on the contrary, plating solution with plating reagent It is deposited on base material and is exhausted substantially, so as to which the thickness for making metal film is fixed.Conductive supporting agent can be by pipeline 180 from plating Unit 175 is covered to take out.

According to the system of Fig. 7, the pelletizing through sintering or proppant that are taken out by pipeline 171 from sintering equipment 170 can be with Activated solution is contacted to provide activated proppant.It is cooled down for example, proppant can be introduced in by the proppant of pipeline 171 In device 172, activated solution is applied on proppant to pass through pipeline in any suitable manner in proppant cooler 172 174 provide the activation proppant through cooling.For example, activated solution can be by being located at one inside proppant cooler 172 Or multiple spray nozzle (not shown) are sprayed onto on the proppant in proppant cooler 172, to provide warp by pipeline 174 The activation proppant of cooling.Proppant cooler 172 can be or can include rotary cooler.Rotary cooler can position Near sintering equipment 170.Proppant cooler 172 can be at about 0 DEG C to about 500 DEG C, about 25 DEG C to about 250 DEG C or about 50 DEG C To operating about 5 seconds, about 15 seconds, about 30 seconds or about 1 minute to about 5 minutes, about 10 minutes, about 20 points at a temperature of about 150 DEG C Clock or the period of about 90 minutes.

Some embodiments according to the present invention, conductive material are applied on the proppant according to the system production of Fig. 5-7. For example, the pelletizing through sintering or proppant that take out from sintering equipment 170 and/or proppant cooler 172 be directed into It in plating unit 175 and is dipped into the plating solution being arranged in plating unit 175, which can be included in about 55 DEG C -95 Temperature between DEG C or between about 25-65 DEG C.The dipping time of about 1 to about 30 minute, which can generate, to be deposited on substrate surface Thickness be about 0.05 micron, about 0.1 micron, about 0.25 micron or about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or About 5 microns or thicker of nickel film.Plating solution can continuously supply to give the plating chemical concentrations kept constant or opposite again Ground, plating solution are exhausted substantially as plating reagent is deposited on base material, so as to which the thickness for making metal film is fixed.Conductive supporting agent It can be taken out by pipeline 180 from plating unit 175.

In one or more exemplary embodiments, green pellets and/or proppant through sintering can be molten in contact activation It is adjusted in any step before liquid with adjusting solution disclosed herein.For example, green pellets and/or proppant can contact Adjusting solution in Fluidizer 130,430 is to provide green pellets after the adjustment.Then green pellets and/or proppant after the adjustment may be used To contact activated solution according to the system of Fig. 5-7.For example, adjust solution can be introduced into elevator 155, screening system 160, It is pre-sintered during, before device 165, and/or sintering equipment 170 or contacts green pellets later to provide green pellets after the adjustment. Adjusting solution can in any suitable manner be applied on green pellets and/or proppant.It can be sprayed for example, adjusting solution It applies or is otherwise injected on green pellets and/or proppant.In another example, green pellets and/or proppant can be with Contact adjusts liquid stream or the bath of liquid of solution to provide green pellets after the adjustment.

Fig. 8 is the signal for being used to be prepared the drippage casting system of the substantially particle of spheroidal as described herein by slurry Figure.As shown in figure 8, ceramic raw material, which passes through, pulverizer 105 and is fed to blunger 110, in blunger 110 ceramic raw material, Water, dispersant, and/or pH adjust reagent and are mixed until forming slurry.Slurry is fed to from blunger 110 in tank 115, Slurry is continuously stirred in tank 115 and adds in adhesive.Slurry is fed to heat exchanger 120, heat exchanger 120 from tank 115 Slurry is heated to required temperature.Slurry is fed to pumping system 125 from heat exchanger 120, slurry is fed to by pumping system 125 Head tank 702.Nozzle 704 receives slurry from head tank 704, which, which contains, is suspended in water or any other suitable aqueous solution In ceramic raw material.The pressure slurry of head tank 702 is applied to selected speed by pressure suppling system (not shown) Rate flows through nozzle 704 to form drop.It is the solidification container (coagulationvessel) for receiving drop below nozzle 704 706.Vibrator units (not shown) is connected to nozzle 704 and is used for nozzle or directly in the slurry of flow nozzle 704 Supply pressure pulse.The vibration that the stream of slurry of nozzle 704 generates is flowed through so that leaving the stream of nozzle 704 as drop is from nozzle The drop of uniform-dimension is broken into 704 atmosphere for falling and entering around nozzle 704.Surrounding atmosphere may include any suitable Gaseous medium, such as air or nitrogen.When drop is fallen to solidification container 706, surface tension effect tends to droplet formation For sphere.These drops to fall or sphere and then the upper liquid surface for contacting solidifying liq contained in solidification container 706.Liquid It drops in solidifying liq and solidifies and formed green pellets.Green pellets is formed, therefore anti-not needing to sol-gel in container is solidified Should, reaction gas freely fall area, reaction liquid foaming layer or enter react bath of liquid before reaction liquid is being directed to liquid It is formed in the case of in drop.

Slurry in head tank 702 can have any suitable solid content.The solid content of slurry can about 15%, In the range of about 20%, about 25% or about 35% to about 55%, about 65%, about 75% or about 85%.In one or more examples In property embodiment, solid content can be about 25% to about 75%.The viscosity of slurry can be about 1, about 10, about 25, about 50, about 100 or about 250 to about 500, about 750, about 1,000, about 2,500 centipoises (cP) or higher.The viscosity of adjustment slurry helps to change The formation of kind droplet formation and spheric granules.The viscosity of slurry can pass through the choosing to reactant type and/or reactant concentration It selects to optimize or adjust.The optimization of Dispersant types and concentration can also reduce the viscosity of slurry.Dispersant can be based on Cost, availability and the validity of the viscosity of slurry selected by reduction selects.It can be used for reducing the dispersant of the viscosity of slurry Including sodium metasilicate, ammonium polyacrylate, sodium polymethacrylate, sodium citrate, poly- sodium sulfonate and calgon.

Slurry in head tank 702 can also include any suitable reactant, will be with solidifying the solidification in container 706 Component reaction in liquid is to form semisolid or insoluble compound.This reactant can be or can include monosaccharide, disaccharides, Polysaccharide, citric acid, methylcellulose, polyvinyl alcohol, polyvinyl acetate or borate fluids, or any combination thereof or mixing Object.In one or more exemplary embodiments, reactant is polysaccharide, for example, sodium alginate.Sodium alginate is that one kind is naturally deposited Polysaccharide, water is dissolved in the form of sodium salt, but be crosslinked the gel to form calcium salt forms.

In one or more exemplary embodiments, reactant can be or can include having appointing for divalent exchange mechanism What suitable polymer or copolymer.Reactant can be or can include poly- (ethylene oxide), ethylene-vinyl acetate c Object, carboxylic acid polyalcohol and copolymer, acrylate polymer and copolymer and methacrylate polymers and copolymer. In one or more exemplary embodiments, reactant can be or can include any suitable diatomic polymer or copolymerization Object.In one or more exemplary embodiments, reactant can be or can include poly- (maleic acid) (PMA), poly- (propylene Acid) (PAA), or any combination thereof.For example, reactant can be or can include PMA：PAA copolymers.

Slurry can include any suitable reactant.Slurry can have about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.25wt%, about 0.5wt%, about 0.8wt%, about 1.2wt% or about 1.5wt% to about 1.8wt%, about The reactant concentration of 2wt%, about 2.5wt%, about 3wt%, about 4wt%, about 5wt%, about 6wt% or about 8wt%.At one Or in multiple exemplary embodiments, slurry reaction object concentration can be about 0.2wt% to about 4wt%, about 0.4wt% to about 2.8wt%, about 0.6wt% are to about 2.4wt%, about 0.8wt% to about 1.8wt% or about 1.2wt% to about 1.6wt%.

Solidification tank 706 can contain the solidification liquid for making the reactant chemicals gelatinization in slurry.In other words, solidification liquid can To include making any suitable coagulator of reactant gelatinization.Coagulator can also be or can include being suitble to carry out with reactant Any cationic materials of ion exchange.Coagulator can be or can include divalent, trivalent or more high price cationic materials. In one or more exemplary embodiments, coagulator can be or can include calcium, magnesium, strontium, aluminium, and/or iron one kind or A variety of salt.For example, coagulator can be or can include one or more in calcium chloride, magnesium chloride etc..Solidification liquid can be Or the aqueous solution containing coagulator can be included.Solidification liquid can have about 0.01wt%, about 0.05wt%, about 0.1wt%, about 0.5wt%, about 1wt%, about 2wt% or about 4wt% are to about 6wt%, about 8wt%, about 10wt%, about 15wt% or about The coagulant concentration of 20wt% or more.In one or more exemplary embodiments, the solidification liquid for sodium alginate is dense The calcium chloride solution that it is 0.5wt% to 10wt% that degree is horizontal.

In one or more exemplary embodiments, solidify tank 706 in solidification liquid can include coagulator, reducing agent, And/or conductive material.In one or more exemplary embodiments, slurry disclosed herein can also include reducing agent and/or Conductive material.

The adjustment diameter of nozzle 704, the viscosity of slurry, the ceramic particle content of slurry, for slurry to be fed to nozzle Pressure and by vibration source apply vibration frequency and amplitude, with generate with desired size drop.These variables are excellent Choosing is set as steady state value, because sphere is generated to be formed the pelletizing of a collection of proppant material.It can produce with different sizes Pelletizing different batches.Preferably, every batch of will be single size (that is, being included on single sieve, for example, passing through 20 mesh It sieves but stays on 25 mesh sieve).Adjust the laminar flow for slurry to be fed to the pressure of nozzle to generate across nozzle.Feed pressure Range can be 1 between 50psi.Frequency is adjusted for every group of slurry conditions so that is generated in the stream of slurry for leaving nozzle Resonance, then generates spherical droplets.Frequency range can be between 10 to 20,000 hertz.Iteratively optimization pressure and frequency with Generate uniform spheroid form.Amplitude is adjusted to improve the uniform shapes of formed spherical droplets.Pass through the slurry of nozzle Flow is the function of nozzle diameter, slurry feed pressure and slurry properties (for example, viscosity and density).For example, for by straight Diameter is up to the kaolin and alumina slurry of 500 microns of nozzle, and the flow of each nozzle can be in the model of 0.2-3kg/ hours In enclosing, this is equivalent to about 1 to about 15kg/ (mm²× hour) mass flux.

Nozzle 704 is selected with solidifying the distance between liquid top in container 706, drop to be allowed to reach liquid top Become spherical before portion.The distance can be 1 to 20 centimetre, but be more typically 1 to 5 centimetre, to reduce and liquid surface The deformation of droplet profile during collision, so as to remove for reaction gas, froth bed or before drop enters solidification container 706 The demand of tangentially directed reaction liquid.Reactant chemical substance in the drop of slurry and the solidification liquid in solidification container 706 Precursor reactant, and semi-solid surface is formed on drop, this helps to maintain spherical form and prevents pelletizing from assembling.Preferably, Residence time of the pelletizing in container 706 is solidified is enough to make pelletizing to become enough to firm, so as to prevent they being removed and Spherical deformation occurs during by drying, is semirigid.In some embodiments, pelletizing can fall into vertical upflow In solidifying liq solution so that particle longer is stopped by the sedimentation of liquid by being delayed by with generate in container 706 is solidified Stay the time.

The green pellets formed using the drippage casting system of Fig. 8 can be washed to remove extra coagulator and defeated Be sent to other equipment, in such devices they can with (one or more) adjusting solution disclosed herein and/or (it is a kind of or It is a variety of) activated solution contact with provide after the adjustment and/or activation green pellets.It is raw in one or more exemplary embodiments Pelletizing can be contacted with the activated solution by pipeline 708 from activated solution tank or container (not shown).Green pellets can be with Activated solution is contacted in any suitable manner.For example, can be sprayed-on by the activated solution of pipeline 708 or otherwise It is ejected on green pellets to provide activated green pellets.Green pellets can also contact liquid stream or the bath of liquid of activated solution to provide Activated green pellets.In one or more exemplary embodiments, it can dry and/or calcine in device 165 is pre-sintered Then activated green pellets is sintered green pellets in sintering equipment 170, oxidized with catalytically-active materials to provide Green pellets and/or proppant.

The oxidized green pellets or proppant taken out from sintering equipment 170 can be introduced in plating unit 175 simultaneously It is dipped into the plating solution being arranged in plating unit 175, which may include between about 55 DEG C to 95 DEG C or at about 25 DEG C extremely Temperature between 65 DEG C.It is about 0.05 that the dipping time of about 1 to about 30 minute, which can generate the thickness of deposition on substrate surface, Micron, about 0.1 micron, about 0.25 micron or about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or about 5 microns or more Thick nickel film.Plating solution can by continuously again for give the plating chemical concentrations kept constant or on the contrary, plating solution with plating It covers reagent deposition to be exhausted substantially on base material, orders proppant so as to which the thickness for making metal film is fixed and generated.The conduction Proppant can be taken out by pipeline 180 from plating unit 175.

Fig. 9 depicts the revision of the drippage casting system of Fig. 8, wherein pelletizing or proppant through sintering are via pipeline 171 take out from sintering equipment 170 to contact the activated solution in proppant cooler 172, so as to by pipeline 174 from activation NaOH solution tank NaOH or container (not shown) provide activated proppant.It for example, can be by being located inside proppant cooler 172 One or more nozzle (not shown) spray to activated solution on the proppant in proppant cooler 172, to pass through pipeline 174 provide the activation proppant through cooling.Proppant cooler 172 can be or can include rotary cooler.It can be with Activated solution is introduced directly into spray nozzle or is combined with any suitable dilute solution (for example, water), it is rotary cold to control But the spray rate in device, spraying concentration, spray distance and spraying distribution.Nozzle can be selected in rotary cooler Position, to accurately control the temperature of the proppant contacted with activated solution, and thus accurately in control proppant surface The rate of drying of activated solution.Rotary cooler can be located near sintering equipment 170.Proppant cooler 172 can be Operated at a temperature of about 0 DEG C to about 500 DEG C, about 25 DEG C to about 250 DEG C or about 50 DEG C to about 150 DEG C about 5 seconds, about 15 seconds, about 30 The period of second or about 1 minute to about 5 minutes, about 10 minutes, about 20 minutes or about 90 minutes.By pipeline 174 from support The activated proppant that agent cooler 172 takes out, which be directed into plating unit 175 and be dipped into, is arranged on plating unit In plating solution in 175, which can be included in the temperature between about 55 DEG C to 95 DEG C or between about 25 DEG C to 65 DEG C.Dipping The time of about 1 to about 30 minute can generate deposition thickness on substrate surface be about 0.05 micron, about 0.1 micron, about 0.25 micron or about 0.5 micron to about 1 micron, about 2 microns, about 3 microns or about 5 microns or thicker of nickel film.Plating solution can be with It continuously is supplied to give the plating chemical concentrations kept constant again or on the contrary, plating solution is deposited on base material with plating reagent It is above exhausted substantially, so as to which the thickness for making metal film is fixed and generates conductive supporting agent.The conductive supporting agent can pass through pipe Line 180 takes out from plating unit 175.

In one or more exemplary embodiments, green pellets and/or the proppant through sintering can be being immersed from plating It is handled in activated solution disclosed herein bath in any step before covering the plating solution of unit 175.Activated solution can be with Any suitable mode is applied in green pellets and/or proppant.It for example, can be according to the system of Fig. 8 and Fig. 9 by activated solution Spraying is otherwise ejected on green pellets and/or proppant.In another example, green pellets and/or proppant can be with The liquid stream or bath of liquid of activated solution are contacted before plating solution is immersed.

In one or more exemplary embodiments, green pellets and/or proppant through sintering can be according to Fig. 8 and figure It is adjusted in any step before 9 system contact activated solution with adjusting solution disclosed herein.Adjusting solution can be with It is applied in any suitable manner on green pellets and/or proppant.For example, adjusting solution can be sprayed-on or with its other party Formula is ejected on green pellets and/or proppant.In another example, green pellets and/or proppant, which can contact, adjusts solution Liquid stream or bath of liquid, to provide green pellets after the adjustment.

In one or more exemplary embodiments, plating unit 175 disclosed herein can include being suitable for any conjunction One or more nozzle (not shown) that plating solution is sprayed or be atomised on proppant by suitable mode.One or more exemplary In embodiment, plating unit 175 can be added or replace with to spray to plating solution into one on green pellets and/or proppant A or multiple nozzles.For example, nozzle can be located at any suitable stage of any processing shown in Fig. 4-9.It is filled being pre-sintered Before putting 165 and/or sintering equipment 170, during, or after, plating solution can be sprayed to green pellets, the green-ball through calcining by nozzle On group, dried green pellets, and/or supporter through sintering.

Figure 10 is the diagram of the spray nozzle device 800 of drippage casting nozzle 802 for including being arranged in processing nozzle 804.Drop End 810 can be included by falling casting nozzle 802, and slurry drop is discharged from the end 810.In one or more exemplary embodiments In, drippage casting nozzle 802 can be same or similar with nozzle 704.Drippage casting nozzle 802 can be arranged on processing nozzle In 804 so that processing nozzle 804 circumferentially around drippage casting nozzle 802.It drips casting nozzle 802 and processing nozzle 804 can With axially aligned with each other.There may be gap between the inner surface of processing nozzle 804 and the outer surface of drippage casting nozzle 802 Or annular space 818.Processing nozzle 804 can have any suitable shape.For example, processing nozzle 804 can be or can be with Including cylinder and/or frustoconical body with first end 808 and second end 806.Handle the second end of nozzle 804 806 can be positioned adjacent to the end 810 of drippage casting nozzle 802.

It, can be by liquid (for example, (one or more) adjusting solution disclosed herein and/or (one kind in exemplary operation Or a variety of) activated solution) pass through the direction introducing processing nozzle 804 shown in first end 808 along arrow 814.Liquid can located It manages and liquid film 812 is formed on the inner surface of nozzle 804, which flows to the by least part of annular space 818 Two ends 806.When liquid film 812 is close to second end 806, liquid film contacts and surrounds the liquid for leaving drippage casting nozzle 802 It drips to provide coated drop 816.Coated drop 816 is fallen subsequently into solidification container, is applied in container is solidified The drop 816 covered is partially cured to form drips the activated of casting method according to (one or more) disclosed herein And/or the green pellets adjusted.

Figure 11 is the spray nozzle device for including being arranged on the drippage casting nozzle 902 in the processing nozzle 904 with entrance 915 900 diagram.Figure 12 depicts the vertical view of spray nozzle device 900, shows the entrance 915 tangentially coupled with processing nozzle 904. End 910 can be included by dripping casting nozzle 902, and wherein slurry drop is discharged from the end 910.One or more exemplary In embodiment, drippage casting nozzle 902 can be same or similar with nozzle 704,802.Place can be surrounded by dripping casting nozzle 902 Reason nozzle 904 is arranged.It drips casting nozzle 902 and processing nozzle 904 can be axially aligned with each other.In processing nozzle 904 There may be gap or annular space 918 between surface and the outer surface for dripping casting nozzle 902.Processing nozzle 904 can have There is any suitable shape.For example, processing nozzle 904 can be or can include having first end 908 and second end 906 Cylindrical and/or frustoconical body.The second end 906 of processing nozzle 904 can be positioned adjacent to drippage casting nozzle 902 end 910.

In exemplary operation, liquid is (for example, (one or more) adjusting solution disclosed herein and/or (a kind of or more Kind) activated solution) by entrance 915 be introduced tangentially into processing nozzle 904, wherein entrance 915 is in the direction as shown in arrow 914 It is upper to be coupled to processing nozzle 904 glibly close to first end 908.Liquid can be formed on the inner surface of processing nozzle 904 Liquid film, the liquid film flow to second end 906 by least part of annular space 918 in the form of being vortexed, such as arrow 912 It is shown.When liquid film reaches second end 906, liquid film, which is contacted and surrounded, leaves the drop of drippage casting nozzle 902 to carry For coated drop 916.Coated drop 916 is fallen subsequently into solidification container, the liquid being coated in container is solidified Drop 916 is partially cured to form according to the activated of (one or more) drippage casting methods disclosed herein and/or is adjusted The green pellets of section.Electromagnetic method described herein, which is included at or near the crack of depths, to be powered to ground, and measure earth table Electrically and magnetically response in face or adjacent well/drilling.Electromagnetic method described herein is usually with cased wellbores (for example, institute in Figure 13 The well 20 shown) it is used in combination.Specifically, casing 22 extends in well 20, and well 20 extends through in a manner of with three-dimensional component Cross geological stratification 24a-24d and 24f-24i.

Referring now to figure in fig. 14 it is shown that phantom, wherein producing well 20 extend vertically down through one Or multiple geological stratification 24a-24d and 24f-24i and horizontal-extending in layer 24i.Although well is typically vertical, herein The electromagnetic method of description is not limited to be used together with vertical well.Therefore, term " vertical " and " level " in its reference general It is used to be directed toward the well of various orientations in meaning.

It can include hole 26 being bored into desired depth for the preparation of the producing well 20 of hydraulic fracturing, then at some In the case of horizontally extend hole 26 so that hole 26 have any desired degree vertically and horizontally component.Casing 22 can be by water Mud 28 is fixed in well 20 to seal hole 26 from the geological stratification 24a-24d and 24f-24i in Figure 14.Casing 22 can have more A perforation 30 and/or sliding sleeve (not shown).Perforation 30 is as shown in figure 14, in the horizontal component of well 20, but ability Domain skilled artisan will realize that, perforation can be located at along hole 26 at any desired depth or horizontal distance, but usual Positioned at the position in the region of the hydrocarbon-containiproducts in geological stratification 24, can in one or more geological stratification 24a-24d and In 24f-24i.Ordinary skill technical staff will also be appreciated that well 20 can not include casing, for example, in trepanning well In the case of.The region of hydrocarbon-containiproducts can contain oil and/or gas and other fluids and material with fluid-like characteristics Material.The region of hydrocarbon-containiproducts in geological stratification 24a-24d and 24f-24i by with enough rate and pressure by fluid pump It is sent in casing 22 and across perforation 30 and by hydrofracturing fault, to generate crack 32, then when for generating the hydraulic pressure in crack 32 When being released, conductive supporting agent is mixed in fluid, conductive supporting agent will strut generated crack 32.

Hydraulic fracture 32 shown in Figure 14, to be radially orientated far from 22 ground of metal casing.This orientation is substantially It is exemplary.In practice, waterpower induction crack 32 can as shown in figure 14 radially, laterally or the two it Between be orientated.Various orientations are all exemplary, and be not intended to and define or limit electromagnetic method as described herein in any way.

The certain embodiments of electromagnetic method according to the present invention, as shown in exemplary in Figure 15, electric current has by seven strands Line insulated cable 34 is (for example, those of ordinary skill in the art can be from Camesa Wire, Rochester Wire and Cable, Inc., WireLine Works, Novametal Group and Quality Wireline＆Cable Inc. are widely It is commercially-available) and the 10 of perforation 30 meters be usually located in casing 22 are sent to along wellbore 20 or bigger (is higher than or low In) energization point at distance.In other exemplary embodiments, wired insulated cable 34 can include 1 to 6 strand or 8 strands or more Multiply.The sinker 36 of wire cable 34 is connected in contact with or close to casing 22, then casing 22, which becomes, generates underground electricity Field and the electric current line source in magnetic field.In other exemplary embodiments, other than sinker 26 or instead of sinker 26, You Xian electricity Cable 34 may be connected to or be otherwise attach to centralizer and/or any other suitable downhole tool.These with Crack 32 containing conductive supporting agent interact with generate by for detect, position and characterize proppant fill crack 32 Secondary electric field and magnetic field.

The some embodiments of electromagnetic method according to the present invention, as schematically depicted in fig. 15, Electric control case 40 pass through Cable 42 is connect with casing 22 so that by injecting a current into crack well 20 in well head direct-electrifying casing 22.In a reality It applies in example, power control case 40 is connected wirelessly to the receiver/transmitter on equipment truck 41 by receiver/transmitter 43 39.It will be appreciated by those of ordinary skill in the art that other appropriate devices that electric current is transmitted to the point that is powered can also be used.

As seen in figs. 15-17, multiple electric fields and magnetic field sensor 38 will be located at the earth with rectangle or other suitable arrays On surface, 32 area above of crack is covered around crack well 20 and is expected.In one embodiment, sensor 38 wirelessly connects The receiver/transmitter 39 being connected on equipment truck 41.The full-size of array (slot) should usually be at least crack area The 80% of depth.Sensor 38 responds x, y and z-component for measuring electric field and magnetic field.These responses will be used by and number The data that value is simulated and/or inverting measures are compared to infer position and the characterization of conductive supporting agent, to determine coming for response Source.The response of electric field and magnetic-field component will depend on：The orientation of crack well 20, the orientation in crack 32, layer 24a-24d and 24f- Conductivity, magnetic permeability, the capacitivity of 24i, conductivity, magnetic permeability, capacitivity and the proppant in the crack 32 of proppant filling are filled out The volume in crack 32 filled.In addition, the conductance of the geological stratification between surface and target forming layer 24a-24d and 24f-24i Rate, magnetic permeability and capacitivity influence the response of record.From the response recorded on the spot, it may be determined that proppant fills crack 32 Details.

In another embodiment, electrically and magnetically sensor can be located in adjacent well/drilling.

Depending on the conductivity of the earth for surrounding casing 22, when electric current flow back into surface along casing 22, electric current It can be uniform or can be non-uniform.According to two embodiments as shown in figure 15, along wellbore 20 (for example, along Path 50 or 52) current leakage occurs and returns to the electrical ground 54 established at well head.Such as submitted within 9th in August in 2011 Entitled " Simulating Current Flow Through a Well Casing and an Induced Fracture " U.S. Patent application No.13/206, described in 041 (entire contents are incorporated herein by reference), casing is in number According to analysis and numerical simulation in be represented as leakage transmission line.Numerical simulation shows that (conductivity is greater than about for the conductive earth 0.05 every meter of Siemens (S/m)), electric current would leak into stratum, and if conductivity is less than about 0.05S/m, electric current general or more Or less evenly along casing 22.As illustrated in figures 18 a and 18b, in order to which electric current is located in casing 22, Ke Yian Fill electric insulating tube connector or trunnion ring.It, can be by by 60 He of matching surface of connector according to implementation as shown in Figure 18 A 62 materials 64 of the coating with high dielectric strength install insulating joint, such as with dielectric strength and with being suitable for being adhered to To be maintained at the appropriate location between engagement surface tough and tensile and flexible it is known that and commercially available modeling on engagement surface Material or resin material.Such as United States Patent (USP) No.2, described in 940,787, the entire disclosure is incorporated herein by reference, this Plastics or resin material include epoxy resin, phenolic resin, rubber composition and alkyd resin nd various combinations thereof.Additional materials Including polyetherimide and Noryl.According to embodiment as shown in figure 18b, the abutting end 70 and 72 of connector is exhausted with electricity The set trunnion ring 74 of edge engages.Transmission line expression can handle various casing situations, such as only vertical, inclined well, cover The vertically and horizontally part of pipe and single or multiple clearance for insulations.

Detection, positioning and the characterization of conductive supporting agent in crack will depend on several factors, including but not limited to crack Net conductivity is broken volume, conductivity, the magnetic permeability of the earth between the sensor of around crack and crack and surface installation And capacitivity.The net conductivity in crack refers to crack, proppant and the stream when crack, proppant and fluid are both placed in ground The combination of bulk conductivity subtracts the conductivity of the earth in the absence of crack, proppant and fluid.In addition, proppant fills crack Total conductivity be following combination：The conductivity generated by manufacturing fracture is added plus the conductivity of new/modified proppant The conductivity of fluid, in addition moving fluid through the electro kinetic effect of porous body such as proppant pack.It can be by being multiplied by The height of fracture, length and width (i.e. gap) determine the volume in the crack of the over-simplification of the plane with geometry. Three-dimensional (3D) the finite difference electromagnetic calculation of solution Maxwell's electromagnetic equation can be used to carry out numerical simulation.In order in earth table Face can detect the electromagnetic response in the crack of depth proppant filling, be about 38 cubic metres for total crevice volume For Barnett shale original mold types, the net crack conductivity in a computing unit of finite difference (FD) grid, which is multiplied by, to be split Seam volume has to be larger than about 100Sm².For Barnett shale models, penetration of fracture 2000m.The these requirements of numerical simulation The attribute in the field application of the earth in addition to Barnett shale can be converted to.

Electromagnetism (EM) wave field is determined by the propagation and/or diffusion of three-dimensional (3D) geologic medium by the electromagnetic equation of Maxwell It is fixed.

According to one embodiment of present invention, (inversion algorithm and electromagnetism such as based on Maxwell equation can be used Migration and/or holography) imaging method analyzes the three-dimensional component of the electric field of measurement and magnetic responsiveness, to determine proppant pack The position of layer.The data inversion of acquisition with determine proppant pack position be related to adjust earth model parameter, including but it is unlimited In the proppant position in crack and the net conductivity in crack, with the earth model for obtaining best fit to promote to a hypothesis Response model calculate.Such as Bartel, L.C., Integral wave-migration method applied to Electromagnetic data, SEG Technical Program Expanded Abstracts, 1994,361-364 institutes It states, electromagnetism integration wave moving method is using Gauss theorem, wherein being supported by the data projection that aperture obtains to underground with being formed The image of agent filling layer.In addition, such as Bartel, L.C., Application of EM Holographic Methods to Borehole Vertical Electric Source Data to Map a Fuel Oil Spill,SEG Technical Program Expanded Abstracts, described in 1987,49-51, electromagnetism holographic method is based on seismic holography method, and relies on In constructive interference and destructive interference, wherein data and source waveform project in earth volume to form the figure of proppant pack Picture.Due to the long wavelength for being used to migrate and the low frequency electromagnetic of holographic method responds, it may be necessary to it is shorter to convert the data into wavelength Another domain.Such as Lee, K.H., et al., A new approach to modeling the electromagnetic Response of conductive media, Geophysics, Vol.54, No.9 (1989) are described, which is referred to as q Domain.In addition, such as Lee, K.H., etal., Tomographic Imaging of Electrical Conductivity Using Low-Frequency Electromagnetic Fields, Lawrence Berkeley Lab, described in 1992, when application becomes When changing, wavelength changes.

In addition, the constitutive relation of the electromagnetic equation of combination Maxwell isotropic medium unrelated with being suitable for the time generates It is referred to as the system of the first order partial differential equation of six couplings of " EH " system.The title comes from dependent variable wherein included, That is electric vector E and magnetic vector H.Coefficient in EH systems is three kinds of material characters, i.e. electric current conductivity, magnetic permeability and capacitivity. All these parameters can change with 3d space position.Inhomogeneities in EH systems represents the various body sources of electromagnetic wave, packet Include conduction current source, magnetic induction source and displacement current source.Current source is conducted, represents the electric current in electric wire, cable and borehole casing, It is most common source in live electromagnetic data acquisition experiment.

Three components and magnetic vector for electric vector E are solved using explicit Fdtd Method (FD) numerical method The EH systems of three components of H, as position and the function of time.The three-dimensional grid of electromagnetic medium parameter is needed to represent (to be claimed For " earth model "), and it can be built by available geophysical log and geological information.The amplitude of current source, direction It is also input in algorithm with waveform.Waveform can have the shape (such as in Gaussian pulse) of similar pulse or can be Repetition square wave comprising positive polarity and negative polarity portion, but it is not limited to the two particular options.The execution of digital algorithm is to be distributed The form of time series recorded on grid earth model or at internal receiver position generates electromagnetic response.These responses Represent three components or its time derivative of E or H-vector.

Repeating for Finity difference numberical algorithm makes it possible in important modeling parameters variation, to electromagnetic response Size (magnitude) and frequency content carry out quantitative predication (measuring at the earth's surface or in neighbouring drilling).For example, electric current The depth in source can the variation from shallow to deep.Current source can be positioned on a little or can be the transmission line of spatial spread, Such as the borehole casing of electrification.Source waveform can be broadband or narrowband in spectral content.Finally, thus it is possible to vary electromagnetism earth mould Type is possibly used for assessing the screen effect of shallow conductive layer.The purpose of this modeling activities is the recorded electromagnetic data pair of assessment The sensibility of relevant parameter variation.In turn, for designing best on-site data gathering mode, these modes have this information Enhance potentiality, the crack of proppant filling can be imaged in depth.

Electrically and magnetically response can change with input current amplitude.It, can in order to obtain the response for being higher than background electromagnetic noise It can need the high current of 10 to 100 amperes of orders of magnitude.Impedance and ground resistance of the cable to current contact point will determine to obtain institute Voltage needed for expectation electric current.It is expected that contact resistance very little, will not occupy required voltage.Furthermore, it may be necessary to many heavy Multiple measurement data sums to obtain measurable signal level on noise level.It applies at the scene and scene modeling In, temporal current source waveform can be used.Typical time domain waveform by forming as follows：The turn-on time of positive current is followed by breaking ETAD expected time of arrival and departure, followed by the turn-on time of negative current.In other words ,+electric current, is then shut off, then then-electric current turns off.It will The repetition rate used will be by such as making decision：Electric current has to last for how long can be only achieved stable state or electrical current It needs how long to stop until field disappears or almost nil.In the illustrative methods, steady-state value and current cut-off will be used Collapsing field later analyzes measured response.The advantages of analyzing data when electrical current is zero (collapsing field) is, main The response of field contribution (coming spontaneous emission conductor, i.e. casing) has been eliminated, and only measures earth response.In addition, time domain inputs The closing period of signal allow analysis may the DC electric field as caused by electrokinesis, including but not limited to flowed in fracturing process Dynamic fluid and proppant.Cracks character (orientation, length, volume, height and asymmetry) will pass through the anti-of the data that measure The holographic reconstruction form of the earth (crack) part of the electroresponse measured or secondary field is drilled and/or generated to determine.According to certain Embodiment will prepare precracking exploration to detach the secondary field caused by crack.Those of ordinary skill in the art will recognize that To other technologies of the electromagnetic data for analysis record, such as the electric current of electromagnetic data observed can also be used Source waveform and Full wave shape reversion.

On-site data gathering experiment is carried out to represent with the transmission line in testing well casing current source.The electric field of calculating and measurement Electric field is consistent.The test shows that the transmission line choke source in Three dimensional finite difference electromagnetic code is realized and gives accurate knot Fruit.Agreement is of course depend upon the accurate model of description earth electromagnetic property.In the experiment of this on-site data gathering, common electricity Mud logging (electrical logs) and builds earth model for the electrical properties of the earth of characterization test wellbore.

Including following embodiment with show the present invention illustrative embodiment.It will be appreciated by the skilled addressee that this Technology disclosed in a little embodiments is merely illustrative rather than restricted.In fact, according to the disclosure, this field is common It will be appreciated by the skilled person that many changes can be carried out in disclosed specific embodiment, and the present invention is not being departed from Spirit and scope in the case of still obtain similar or like result invention.

Example 1

The ceramic proppant of conventional low-density and intermediate density is coated with sheet metal using RF magnetron sputterings, these are often The low-density of rule and the ceramic proppant trade name of intermediate density(CL)20/40、(HP or HYDROPROP) 40/80,20/40 He40/70 derives from the CARBO Ceramics Inc of Houston, Texas.Three kinds of metallic targets are used to sink Product, i.e. aluminium, copper and mickel.Using 200WRF power, the deposition pressure of 5mTorr and the argon background flow velocity of 90sccm are in sputtering chamber It is deposited.There are three 2 inches of hinged target stents, the shapes complicated available for coating for sputtering chamber tool.The system also has rotation The water cooling sample stage turned is configured (sputter-down configuration) with downward sputtering and uses.In coating proppant Before, pass through the deposition rate for the determining three kinds of metals that such as get off：Pass through scanning electron microscope using Zeiss Neon 40SEM (SEM) cross-sectional analysis on metal sputtering to silicon wafer and will measure coating layer thickness.

Proppant is loaded into the sputtering chamber in the aluminum pot of 12 inch diameters with 1 inch of high side.It applies every time About 130 grams of proppants are used when covering operation.The proppant of the amount substantially provides a mono-layer propping agent on pot bottom.Proppant exists Using 6 inches of long fine wires " stirring " in deposition process, fine wire be suspended in the top of pot and with the proppant in pot Contiguously place.Compared with the coat deposition time determined from silicon wafer coating thickness measurement, coat deposition time increases One times, so as in view of substantially coating proppant on side, they be rolled, be then applied to opposite side.By about 100nm and The coating of about 500nm is deposited on each type of proppant, and each of which is three kinds of metals.

After the coating process, visual and light microscope checks proppant.It is the result shows that relatively thin with about 100nm The proppant of coating has usual non-uniform coating, and the proppant of the relatively thick coating with about 500nm is applied with uniform Layer.

Example 2

Regular low density and Midst density ceramic proppant, can with trade name CARBOLITE 20/40, CARBOHYDROPROP 40/80, CARBOPROP 20/40 and CARBOPROP 40/70 are from Houston, TX CARBO Ceramics Inc. are commercially available, are sensitized and activate by following method：It is immersed in 2.0% stannous chloride solution It middle about 3 minutes, rinses in water, immerses 0.01% palladium chloride solution about 3 minutes, finally cleaning down in water.

Electroless nickel plating plating bath solution is prepared for, wherein closing object, 20g sodium hypophosphites, 11 grams of lemons comprising 25g nickel sulfate hexahydrates Sour sodium dihydrate and 10g sodium acetates/liter distilled water.The pH of plating bath is adjusted to 5 using sulfuric acid, plating bath is then heated to 90 DEG C temperature.Then proppant sample be previously sensitized and activation is added in bathing and coats 1-30 minutes to generate conduction Nickel coating proppant.After coating processes, coated proppant sample is checked visually and by light microscope.

Example 3

Regular low density and Midst density ceramic proppant, can with trade name CARBOLITE 20/40, CARBOHYDROPROP 40/80, CARBOPROP 20/40 and CARBOPROP 40/70 are from Houston, TX CARBO Ceramics, Inc. is commercially available, is sensitized and activates by following method：Immerse 2.0% stannous chloride solution about 3 Minute, it rinses in water, immerses 0.01% palladium chloride solution about 3 minutes, finally cleaning down in water.

Electroless copper plating bath solution is prepared, contains 53 grams of sodium potassium tartrate tetrahydrates, 19 grams of copper sulphate, 13 grams of sodium hydroxides and 21 Gram sodium carbonate/liter distilled water.Then 10-40ml formaldehyde is added in by every liter of concentrate to prepare plating bath.Then plating bath is heated To 45 DEG C.Then the previous proppant for being sensitized and activating is added in bath and coated 1-30 minutes, obtain conductive copper coating Proppant.After coating processes, visually and the proppant sample that is coated by light microscope inspection.

Example 4

In this embodiment, 57 grams of CARBOLITE 20/40 are dipped in 20ml and contain 10mg sodium borohydrides and 1 μ l Tween^TMIn the deionized water of 20 (PEG (20) sorbitan monolaurates).Then by dry in 85 DEG C of baking ovens The mixture is evaporated on particle surface.Then the particle by these dryings is transferred to by Caswell Electroless In the bath that Nickel Plating Kit are formed, the bath is commercially available from the Caswell Inc. of New York Lyons, wherein carrying out immediately Plating.The embodiment shows that the surface of ceramic particle can be activated in the case of without using palladium or other noble metals.It was found that The surface of particle can by the way that particle is immersed in reducing agent solution to activate, the reducing agent solution such as sodium borohydride or Sodium cyanoborohydride, the wherein solution can be dried on particle or can will be transferred to nothing with the particle of the solution-wet Electroplating bath, both of which are enough to induce plating.

Example 5

It has been found that the certain ceramic mixtures for being used to prepare proppant contain the iron oxide or iron fragment of significant amount.This A little iron fragments can be reduced into the elemental iron for having catalytic activity to copper and mickel electroless plating liquid.In this embodiment, by 57 grams CARBOPROP 20/40 is put into alumina boat, it is inserted under 5% hydrogen atmosphere in tube furnace in argon gas.Temperature 700 DEG C are risen to, continues 2 hours, CARBOPROP 20/40 allows to impregnate 2 hours.Allow stove natural cooling, sample is from stove State to be plated is in after middle taking-up.

The embodiment shows by using natural iron content, can be with plating proppant particles, without additional activation Agent, such as Pd.By keep in kiln reducing environment (its can by there are carbon monoxide or partially combusted other products come Characterization), Surface Fe ion reduction can be induced near the end of manufacturing process into atom iron.Iron on proppant particles surface It can also be restored by being exposed to carbon monoxide or hydrogen at elevated temperatures after fabrication, the raised temperature can be with It is about 300 DEG C to about 1100 DEG C.Finally, by the way that particle is placed in the solution of reducing agent such as sodium borohydride, particle can be restored Iron on surface.After being restored in these Surface Fe sites, electroless solution can be used to carry out plating to the particle.

When used as a propping agent, particle as described herein can be handled in a manner of identical with conventional proppants.For example, Grain can be transported to well location with bag or bulk form together with the other materials for frac treatment.Conventional equipment can be used Particle is placed in stratum as proppant with technology.For example, particle is mixed with fracture fluid, it is then poured into stratum In crack in.

Example 6

The planet bench mixer with " B " flat beater and heating mantle can be used to apply conducting polymer coating Trade name CARBOLITE 20/40 and CARBOHYDROPROP40/80 are overlying on from the CARBO in Houston, Texas city The Regular low density ceramic proppant that Ceramics Inc. are bought.Every time about 500g proppants are used during coating operation.Such as following table The coating of the 0.1 weight % and 0.4 weight % of proppant are prepared shown in I：

Table I

In each case, proppant is heated to 150-200 DEG C in an oven, and is added to steel reinforced concrete and closes in bowl.Xiang Jia Adhesion promotor (such as aminopropyltriethoxywerene werene, amino-functional coupling agent and glycidol are added in the proppant of heat Oxygroup propyl trimethoxy silicane), to enhance the combination between inorganic substrate and organic polymer.Mixing bowl is placed in external add In hot jacket, to allow when adding in additive, heat retains in systems." B " flat beater is with the centre of about 280rpm Speed is advanced, while mix bowl and be held in place in circuit orbit along the wall surface side of mixing bowl, so as in short-term It is interior to be thoroughly mixed.Typical batch time table is as shown in following table two：

The coating time table of Table II-on ceramics:

Ingredient	Add in the time
		Base material	0s
Adhesion promotor	7s
		Conducting polymer	15s
Finally recycle	5-10min

It in addition, will by using the planetary-type mixer as described above with " B " flat beater and heating mantle PEDOT:PSS is added to the coating of preparation 0.1% and 0.4% in phenol formaldehyde (PF) (novolaks) coating.Every time during coating operation Use about 500g proppants.For the coating of 0.1% and 0.4% proppant, respectively by the PEDOT of about 42g and 167g:PSS It is added to that (phenolic aldehyde is clear with hexamine (13% hexamine, based on phenol-formaldehyde (novolaks)) crosslinked phenol-formaldehyde with 20g Paint) resin 500g proppants in, with and without adhesion promotor as described above.Typical batch time table such as following table Shown in III：

The coating time table of Table III-ceramics with phenol-formaldehyde resin:

Ingredient	Add in the time
		Base material	0s
Phenol-formaldehyde resin	0s
		Adhesion promotor	7s
Hexamine (crosslinking agent)	30s
		Conducting polymer	1.5-2min
Finally recycle	5-10min

After coating processes, coated proppant sample is checked visually and by light microscope.

Example 7

Measured using the test device shown in Figure 19 the various proppant samples that are prepared according to embodiment 1-3,6 and 7 with And the conductivity of uncoated proppant sample.As shown in figure 19, test system 1000 is 0.5 inch including internal diameter and outer diameter is 1.0 inches of insulating nitride boron mold 1002, is arranged in the hole 1004 in punching block 1006, and the internal diameter in hole 1004 is 1.0 English It is very little.The plug of steel column up and down 1008 and 1010 with 0.5 inch outer diameter is inserted into the upper end 1012 of insulating nitride boron mold 1002 respectively In lower end 1014 so that in the front end 1018 of the upper plug 1008 of insulating nitride boron mold 1002, the front end of lower plunger 1010 Chamber 1016 is formed between 1020 and the inner wall 1022 of boron nitride sleeve 1002.Upper plug 1008 is from insulating nitride boron mold 1002 It removes, proppant is loaded onto in room 1016, until proppant bed 1024 is reached in 1020 height of front end of lower plunger 1010 To about 1 to 2cm.Then upper plug 1008 is reinstalled in insulating nitride boron mold 1002, before upper plug 1008 End 1018 is engaged with proppant 1024.Copper wire 1026 is connected in upper plug 1008 and current source 1028 and voltmeter 1030 The pole of each.Second copper wire 1032 is connected to each in lower plunger 1010 and current source 1028 and voltmeter 1030 Another pole.Current source can be any suitable DC electric current source well known within the skill of those ordinarily skilled, such as DC electric current source Keithley 237High Voltage Source Measurement Unit in pattern, and voltmeter can be ability Any suitable voltmeter known to the those of ordinary skill of domain, such as can be used under the DC mV patterns of certain samples Fluke 175True RMS multimeters for more high-resistance sample, can use ohm table schema.

Power supply is powered, and then determines the resistance of the test system 1000 with proppant bed 1024 in room 1016.Then It using upper plug 1008 and lower plunger 1010 as electrode, and pressure is applied on proppant bed 1024, measured with multimeter The resistance of the proppant 1024 of function as pressure.Specifically, R=V/I is measured from the proppant bed 1024 in room 1016 Value subtracts the resistance of the system with plunger contact, and electricalresistivityρ=R*A/t, wherein A are the faces that proppant bed 1024 occupies Product, t is thickness of the proppant bed 1024 between upper plug 1008 and lower plunger 1010.

As a result it is as follows：

Electric measurement is carried out to the base support agent for being not added with any conductive material on sample under 100V DC, it is described Proppant of the sample for the 50 volume % in wax is pressed into disk of the nominal diameter for 1 inch and about 2mm thickness.Use this The resistivity of pure wax of a little values to calculate resistivity and using measuring, by the volume point for drawing log (resistivity) vs. proppants It counts and is extrapolated to the extrapolated value that volume fraction is 1.

CARBOPROP 40/70：2×10¹²Ohm-cm

CARBOPROP 20/40：0.6×10¹²Ohm-cm

Hydrocarbon：1.8×10¹²Ohm-cm

CARBOECONOPROP：9×10¹²Ohm-cm

It should be noted that the resistivity of the sample of upper planar survey is very high and is not suitable for the detection in the present invention.

To according to embodiment 1 prepare with thickness for 100nm and 500nm aluminized coating base support agent and with The base support agent of 0.1% or 0.4% poly- (3,4- ethyldioxythiophene) (PEDOT) coating carries out electrical measurement, these bases Plinth proppant is with or without amino silane.As a result following table IV and Figure 20 are shown in：

Table IV

It can be seen in figure 20 that using with 500nm thickness aluminized coating CARBOLITE20/40 with CARBOHYDROPROP 40/80 obtains the optimum in terms of electric conductivity.

It is 500nm to carry out the base support agent with different weight percentage and the thickness of aluminized coating prepared according to embodiment 1 This base support agent mixture electrical measurement.As a result it is shown in following Table V and VI and Figure 21-22.

Table V shows CARBOLITEs of the CARBOLITE 20/40 with 500nm aluminized coatings with being not added with conductive material The data of 20/40 mixture.For each sample shown in Table V, 3g specimen materials are placed in 0.5 inch of mold to carry For 0.196 square inch of area.The application electric current each tested is 5mA, and test carries out at room temperature.

Table V

Table VI shows HYDROPROPs of the HYDROPROP 40/80 with 500nm aluminized coatings with being not added with conductive material The data of 40/80 mixture.For each sample shown in Table VI, by 3g specimen materials be placed in 0.5 inch of mold with 0.196 square inch of area is provided.The application electric current each tested is 5mA, and test carries out at room temperature.

Table VI

From Table V and VI and Figure 21-22 as can be seen that regardless of coating or the relative quantity of uncoated proppant, The resistivity of proppant pack tends to the increase of confining pressure and reduces.In addition, with uncoated proppant Relative quantity increases and the relative quantity of the proppant of coating reduces, and the resistivity of proppant pack sharply increases.Finally, it uses The proppant of 100%Al coatings realizes minimum resistivity.Do not coat leads to resistance with the mixture of uncoated proppant Rate measures the proppant for being less than 100%Al coatings.

The electrical measurement of the proppant with nickel and copper coating is also carried out.As a result it is shown in following table VII and Figure 23.Table VII Show the data of the CARBOLITE 20/40 with nickel coating and the CARBOLITE with copper coating 20/40.For table Each sample shown in VII, specimen material is placed in 0.5 inch of mold.The application voltage tested every time is 0.005V.

Table VII

The electrical measurement of the proppant of nickel coating with different thickness is also carried out.As a result lower Table VIII and Figure 24 are shown in In.Table VIII is shown to be applied with the nickel that thickness is 0.27 micron, 0.50 micron, 0.96 micron, 2.47 microns and 3.91 microns The data of the CARBOLITE 20/40 of layer.Sample " 9006 " in Figure 24 becomes oxidation, for the purpose of the present embodiment, Become not conductive enough.For each sample shown in Table VIII, specimen material is placed in 0.5 inch of mold.Experiment every time Application voltage be 0.01V.

Table VIII

Also carry out the electrical measurement of the proppant with nickel and copper coating as the KCl functions exposed.As a result it is shown in down In table ix and Figure 25.Table ix shows the CARBOLITE20/40 with nickel coating and the CARBOLITE with copper coating 20/ 40 data.Each sample is exposed in the 2%KCl solution that pH is 10, temperature is 120 DEG C 0 day, 1 day, 3 days and 7 days.It is right Specimen material is placed under the pressure of 3560psi in 0.5 inch of mold by each sample shown in table.

Table ix

Copper coating is can be seen that from Table VII and Figure 23 to provide than the conductivity of conductivity bigger that is provided by nickel.From table VIII and Figure 24 can be seen that the thickness increase of nickel coating, and the conductivity provided also increases.And from Table VII and VIII and Figure 23 and 24 is as can be seen that equal regardless of coating or the relative quantity of uncoated proppant, the conductivity of proppant pack It tends to the increase of confining pressure and increases.Finally, the conductivity that KCl solution greatly reduces copper facing proppant is exposed to, But to the conductivity of nickel plating proppant almost without significant influence.

In an illustrative methods of fracturing stratum, by hydraulic fluid to be enough to open the rate and pressure in crack wherein In power injection stratum, and with good grounds (one or more) method as described herein will be contained and prepare and have one or more such as The fluid of particle sintering, being substantially spheroidal of property as described herein is injected into crack to prop up in the on-state Crack seam.

The exemplary embodiment of the disclosure further relates to any one or more of paragraphs below：

1. a kind of method for manufacturing conductive supporting agent particle, including：It prepares comprising water, adhesive and salic original The slurry of material；By slurry atomization into drop；The seed of aluminium oxide is included with drop coating, to form multiple green pellets；Make multiple Green pellets is contacted with the activated solution comprising at least one catalytically-active materials, to provide comprising at least one catalytically-active materials Activated green pellets；Activated green pellets is sintered to provide multiple proppant particles, wherein sintering makes catalytic activity material Material oxidation；And multiple proppant particles is made to be contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting Agent particle.

2. according to the method described in paragraph 1, wherein conductive supporting agent particle is included in the outer surface of each proppant particles The thickness of upper formation is the substantially uniform coating of at least conductive material of 10nm.

3. the method according to paragraph 1 or 2, wherein at least one catalytically-active materials be selected from include iron, tin, palladium, silver, And combinations thereof group.

4. according to the method described in paragraph 3, contact of the plurality of green pellets with activated solution includes：It is sprayed with activated solution Green pellets is applied, wherein activated solution is aqueous solution.

5. the method according to any one in paragraph 1 to 4, plurality of green pellets with activated solution before contacting It is contacted with alkaline solutions of the pH more than 8.

6. the method according to either segment in paragraph 1 to 5, wherein conductive material include from including aluminium, tin, zinc, copper, Silver, nickel, gold, platinum, palladium and rhodium group in the metal that selects.

7. according to the method described in paragraph 6, wherein plating solution is the alkaline solution for including nickel.

8. a kind of method for manufacturing conductive supporting agent particle, including：It prepares comprising water, adhesive and salic raw material Slurry；By slurry atomization into drop；Salic seed is coated with drop, to form multiple green pellets；It is sintered green pellets To provide multiple proppant particles；Multiple proppant particles is made to be connect with the activated solution comprising at least one catalytically-active materials It touches, to provide the activated proppant particles for including at least one catalytically-active materials；And make multiple activated supports Agent particle is contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting agent particle.

9. according to the method described in paragraph 8, wherein conductive supporting agent particle is included in the outer surface of each proppant particles The thickness of upper formation is the substantially uniform coating of at least conductive material of 10nm.

10. the method according to paragraph 8 or 9, wherein at least one catalytically-active materials be selected from include iron, tin, palladium, Silver, and combinations thereof group.

11. according to the method described in paragraph 10, contact of the plurality of proppant particles with activated solution is included with activation Solution spraying green pellets, wherein activated solution are aqueous solutions.

12. the method according to either segment in paragraph 8 to 11, plurality of green pellets is more than 8 with pH before sintering Alkaline solution contact.

13. according to the method described in either segment in paragraph 8-12, wherein conductive material include from including aluminium, tin, zinc, copper, Silver, nickel, gold, platinum, palladium and rhodium group in the metal that selects.

14. according to the method described in paragraph 13, wherein it is the alkaline solution for including nickel to plate molten.

15. a kind of method for manufacturing proppant particles, including：The slurry of ceramic raw material is provided, which includes reactant； Slurry is made to flow through nozzle in gas and vibrates slurry simultaneously to form drop；Comprising with the upper surface being in direct contact with gas Liquid container in receive drop, which contains coagulator；Reactant is made to be reacted with coagulator so that reactant solidifies In drop；Drop is transferred out of from liquid；Drop is dried to form green pellets；Make green pellets with living comprising at least one catalysis Property material activated solution contact, include the activated green pellets of at least one catalytically-active materials to provide；And it is selecting Activated green pellets is sintered within the scope of fixed temperature, to form proppant particles.

16. according to the method described in paragraph 15, further include：Make proppant particles and comprising one or more conductive materials Plating solution contacts, to provide conductive supporting agent particle.

17. according to the method described in paragraph 16, wherein conductive supporting agent particle is included in the appearance of each proppant particles The thickness formed on face is the substantially homogeneous coating of at least conductive material of 10nm.

18. the method according to either segment in paragraph 15 to 17, wherein reactant include polysaccharide, polybasic carboxylic acid or it The two.

19. the method according to either segment in paragraph 15 to 18, wherein coagulator include calcium, magnesium, strontium, aluminium or iron One or more salt.

20. the method according to either segment in paragraph 15 to 19, wherein, make slurry at it from nozzle by vibrating nozzle It is vibrated during outflow, and wherein slurry is with about 1 to about 15kg/ (mm²× hour) rate from nozzle flow out.

21. the method according to either segment in paragraph 15 to 20, wherein ceramic raw material, which are selected from, includes bauxite, kaolinite The group of soil, aluminium oxide and their mixture.

22. the method according to either segment in paragraph 15 to 21, wherein at least one catalytically-active materials, which are selected from, to be included Iron, tin, palladium, silver and their group arbitrarily combined.

23. according to the method described in paragraph 22, contact of the plurality of green pellets with activated solution includes using activated solution Green pellets is sprayed, wherein activated solution is aqueous solution.

24. the method according to either segment in paragraph 15 to 23, wherein green pellets before activated solution is contacted with pH Alkaline solution contact more than 8.

25. according to the method described in paragraph 16, wherein conductive material include from including aluminium, tin, zinc, copper, silver, nickel, gold, The metal selected in the group of platinum, palladium and rhodium.

26. according to the method described in paragraph 25, wherein plating solution is the alkaline solution for including nickel.

27. a kind of method for manufacturing conductive supporting agent particle, including：The slurry of ceramic raw material is provided, which contains instead Answer object；Activated solution is provided, which includes at least one catalytically-active materials；Slurry is made to flow through the first spray in gas Mouth vibrates slurry to form drop simultaneously；Activated solution film is made to pass through the second nozzle outflow around first jet；Make activation molten Liquid film and drop contact, to form activated drop；It is received in the container containing the liquid with coagulator activated Drop；Reactant is made to be reacted with coagulator so that reactant is set in activated drop；It is transferred out of from liquid through work The drop of change；Dry activated drop, to form activated green pellets；It is sintered within the scope of selected temperature activated Green pellets, to form proppant particles；And proppant particles is made to be contacted with the plating solution comprising one or more conductive materials, with Conductive supporting agent particle is provided.

28. a kind of method for manufacturing conductive supporting agent particle, including：The slurry of ceramic raw material is provided, which contains instead Answer object；Slurry is made to flow through nozzle in gas and vibrates slurry simultaneously to form drop；Comprising with being in direct contact with gas Drop is received in the container of the liquid of upper surface, which contains coagulator；Reactant is made to be reacted with coagulator so that reacting Object is set in drop；Drop is transferred out of from liquid；Drop is dried to form green pellets；It is sintered within the scope of selected temperature Green pellets is to form multiple proppant particles；Make multiple proppant particles and the activation comprising at least one catalytically-active materials molten Liquid contacts, to provide the activated proppant particles for including at least one catalytically-active materials；And make multiple activated Proppant particles are contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting agent particle.

29. according to the method described in paragraph 28, wherein conductive supporting agent particle is included in the appearance of each proppant particles The thickness formed on face is the substantially uniform coating of at least conductive material of 10nm.

30. the method according to paragraph 28 or 29, wherein reactant include polysaccharide, polybasic carboxylic acid or both.

31. the method according to either segment in paragraph 28 to 30, wherein coagulator include calcium, magnesium, strontium, aluminium or iron One or more salt.

32. the method according to either segment in paragraph 28 to 31, wherein, slurry is made from nozzle stream by vibrating nozzle It is vibrated when going out, and wherein slurry is with about 1 to about 15kg/ (mm²× hour) rate from nozzle flow out.

33. according to the method described in either segment in paragraph 28-32, wherein ceramic raw material be selected from include bauxite, kaolin, The group of aluminium oxide and their mixture.

34. the method according to any one of paragraph 28 to 33, wherein at least one catalytically-active materials, which are selected from, to be included Iron, tin, palladium, silver and their group arbitrarily combined.

35. the method according to either segment in paragraph 28 to 34, plurality of proppant particles and activated solution connect It touches and includes spraying proppant particles with activated solution, wherein activated solution is aqueous solution.

36. the method according to either segment in paragraph 28 to 35, plurality of green pellets is more than 8 with pH before sintering Alkaline solution contact.

37. according to the method described in either segment in paragraph 28-36, wherein conductive material include from including aluminium, tin, zinc, copper, Silver, nickel, gold, platinum, palladium and rhodium group in the metal that selects.

38. according to the method for any one in paragraph 28 to 37, wherein plating solution is the alkaline solution for including nickel.

39. a kind of method for manufacturing conductive supporting agent particle, including：The slurry of ceramic raw material is provided, which contains instead Answer object；Slurry is made to flow through nozzle in gas and vibrates slurry simultaneously to form drop；Comprising with being in direct contact with gas Drop is received in the container of the liquid of upper surface, which contains coagulator, reducing agent and conductive material；Also in original slurry material Conductive material on ceramic raw material；Reactant is made to be reacted with coagulator so that reactant is set in drop；From liquid transfer Remove drop；Drop is dried to form the green pellets containing conductive material；And it is sintered green pellets within the scope of selected temperature To form multiple conductive supporting agent particles.

Foregoing description and embodiment are intended to illustrate invention, and without being limited thereto.It should be appreciated that in the essence for not departing from the present invention In the case of refreshing or range, the present invention can be carry out various modifications.

Claims (20)

1. a kind of method for manufacturing conductive supporting agent particle, including：

Prepare the slurry for including water, adhesive and salic raw material；

By the slurry atomization into drop；

Salic seed is coated with the drop, to form multiple green pellets；

The multiple green pellets is made to be contacted with the activated solution comprising at least one catalytically-active materials, to provide comprising described in extremely A kind of activated green pellets of few catalytically-active materials；

The activated green pellets is sintered to provide multiple proppant particles, wherein, the sintering makes the catalytic activity material Material oxidation；And

The multiple proppant particles is made to be contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting agent Grain.

2. according to the method described in claim 1, wherein, the conductive supporting agent particle is included in each proppant particles Outer surface on the thickness that is formed be at least 10nm the substantially uniform coating of the conductive material.

3. according to the method described in claim 1, wherein, at least one catalytically-active materials be selected from include iron, tin, palladium, Silver, and combinations thereof group.

4. according to the method described in claim 3, wherein, the contact packet of the multiple green pellets and the activated solution It includes：The green pellets is sprayed with the activated solution, wherein the activated solution is aqueous solution.

5. according to the method described in claim 1, wherein, the multiple green pellets before being contacted with the activated solution with pH Alkaline solution contact more than 8.

6. according to the method described in claim 1, wherein, the conductive material is included from including aluminium, tin, zinc, copper, silver, nickel, Gold, platinum, palladium and rhodium group in the metal that selects.

7. according to the method described in claim 6, wherein, the plating solution is the alkaline solution for including nickel.

8. a kind of method for manufacturing conductive supporting agent particle, including：

Prepare the slurry for including water, adhesive and salic raw material；

By the slurry atomization into drop；

Salic seed is coated with the drop, to form multiple green pellets；

The green pellets is sintered, to provide multiple proppant particles；

The multiple proppant particles is made to be contacted with the activated solution comprising at least one catalytically-active materials, to provide comprising institute State the activated proppant particles of at least one catalytically-active materials；And

Multiple activated proppant particles is made to be contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting Agent particle.

9. according to the method described in claim 8, wherein, the conductive supporting agent particle is included in each proppant particles Outer surface on the thickness that is formed be at least 10nm the substantially uniform coating of the conductive material.

10. according to the method described in claim 8, wherein, at least one catalytically-active materials be selected from include iron, tin, palladium, Silver, and combinations thereof group.

11. according to the method described in claim 10, wherein, the multiple proppant particles connect with the described of the activated solution It touches and includes：The green pellets is sprayed with the activated solution, wherein the activated solution is aqueous solution.

12. according to the method described in claim 8, wherein, the multiple green pellets is molten with alkalinity of the pH more than 8 before sintering Liquid contacts.

13. according to the method described in claim 8, wherein, the conductive material include from including aluminium, tin, zinc, copper, silver, nickel, Gold, platinum, palladium and rhodium group in the metal that selects.

14. according to the method for claim 13, wherein, the plating solution is the alkaline solution for including nickel.

15. a kind of method for manufacturing conductive supporting agent particle, including：

The slurry of ceramic raw material is provided, the slurry includes reactant；

The slurry is made to flow through nozzle in gas and vibrates the slurry simultaneously to form drop；

The drop is received in the container comprising the liquid with the upper surface being in direct contact with the gas, the liquid contains There is coagulator；

The reactant is made to be reacted with the coagulator, so that the reactant is set in the drop；

The drop is transferred out of from the liquid；

The drop is dried to form green pellets；

The green pellets is sintered in certain temperature range, to form multiple proppant particles；

The multiple proppant particles is made to be contacted with the activated solution comprising at least one catalytically-active materials, to provide comprising institute State the activated proppant particles of at least one catalytically-active materials；And

Multiple activated proppant particles is made to be contacted with the plating solution comprising one or more conductive materials, to provide conductive supporting Agent particle.

16. according to the method for claim 15, wherein, the conductive supporting agent particle is included in each proppant The substantially uniform coating of the conductive material that the thickness formed on the outer surface of grain is at least 10nm.

17. according to the method for claim 15, wherein, the ceramic raw material, which is selected from, includes bauxite, kaolin, oxidation The group of aluminium and its mixture, wherein the reactant include polysaccharide, polybasic carboxylic acid or both, and the coagulator packet Calcic, magnesium, strontium, aluminium or iron one or more salt.

18. according to the method for claim 15, wherein, it is described at least one catalytically-active materials be selected from include iron, tin, Palladium, silver, and combinations thereof group.

19. according to the method for claim 15, wherein, the multiple proppant particles is made to contact packet with the activated solution It includes：The proppant particles are sprayed with the activated solution, wherein the activated solution is aqueous solution.

20. according to the method for claim 15, wherein, the conductive material include from including aluminium, tin, zinc, copper, silver, nickel, Gold, platinum, palladium and rhodium group in the metal that selects.