CN105793386A

CN105793386A - Flash coating treatments for proppant solids

Info

Publication number: CN105793386A
Application number: CN201480066237.8A
Authority: CN
Inventors: R·麦克丹尼尔; K·德雷克; S·莫纳斯蒂尔瑞欧迪斯; R·巴塞尔
Original assignee: PREFERRED UNLIMITED Inc
Current assignee: PREFERRED UNLIMITED Inc
Priority date: 2013-10-31
Filing date: 2014-10-30
Publication date: 2016-07-20
Also published as: CA2927111A1; HK1222669A1; WO2015066283A1; MX2016005096A

Abstract

Treatment methods for coated or uncoated proppants that can, among other things, control fugitive dust during typical handling procedures with typical transport equipment and/or add functional features to the proppant solid are disclosed herein.

Description

Sudden strain of a muscle painting for proppant solid processes

The cross reference of related application

This application claims the application number in submitting on November 15th, 2013 is 61/904, the application number that the U.S. Provisional Patent Application of 833 and on October 31st, 2013 submit to is 61/898, the priority of the U.S. Provisional Patent Application of 328, the disclosure of each of which is incorporated herein by reference.

Field

Embodiment disclosed herein relates to, for instance the process to coating or uncoated proppant, and described process enables in particular to control airborne dust in adopting the process of typical handling procedure of typical transit equipment and/or increase functional character for proppant solid.

Background

The dust produced by proppant (coating and uncoated) handling has been aspect concerned for many years.Dust can be fulsome thing, healthhazard, and also upsets the production of the gentle product of oil produced during fracturing technology.The existing method controlling dust is also not enough.

Attempt by using additive or increasing the defect that washing solves in proppant production method.But, they can't be still effective while maintaining the required performance (such as flowing and intensity) of proppant.Example such as can find in U.S. Patent No. 7,270,879, and the dust that its display produces is likely to fulsome thing, and should avoid.Additionally, various methods can be used for reducing the impact of dust, it includes such as machinery isolation (such as face shield), ventilation and other is in order to reduce the containment strategy of the dust being exposed in operation.But these methods do not reduce dust, but reduce the impact of dust.

Existing method for reducing dust includes potential dust source is changed into solid, pastel or liquid.But, neither one is suitable for must keeping drying with free-flow with the fracturing propping agents used together with existing pneumatic and dry solid material transfer handling facilities or sand in these.This identical requirement eliminates effectively by fine particle wetting to naked eyes and the application touching obvious perceptible conventional wet process.The humidity of such fine particle solid causes caking, assembles and bring the difficulty of increase to gravity charging discharge system or pneumatic conveying equipment.Other chemical method such as describes in U.S. Patent No. 5,480, No. 584 and U.S. Patent No. 7,270, in No. 879, but the method is not suitable for fracturing propping agents or sand, because proppant can lump, assemble or otherwise their free-flowing character of material alterations so that conventional pneumatic conveying equipment presents effect and goes down or lose.Described method without be have very much cost-benefit.

Therefore, there is unique process and control problem relative to the dust of other form in the proppant dust kicked up.Such as, road surfaces is usually fixed in place, such that it is able to application processes and allows process a period of time permeate and solidify.Similarly, fixing process surface is seen in colliery.Proppant often moves often through gravity dumping or pneumatic conveying, and is largely dependent upon free-pouring form to load or discharging with conventional dock equipment.Proppant should be also and have the fracturing fluid of considerably complicated process based prediction model chemically compatible and can be moistening thus working by it.Therefore, the traditional form of dust Control is effective not when for proppant.Accordingly, there exist the demand to improved products and method for controlling dust.Additionally, there are by comprising the functionalized proppant of functional molecules in any coating be applied to proppant to control the demand of dust.Embodiment disclosed herein meets these demands and other demand.

Summary of the invention

Embodiment disclosed herein provides the method for adopting the liquid treating agent of formation and the release that can suppress or reduce dust to process proppant solid (that be such as coated with or uncoated fracturing sand, Alumina, pottery etc.).In some embodiments, when processed solid is used as the proppant in well, described method can not adversely affect the wettability of processed solid, free-flowing character or proppant performance.

Embodiment disclosed herein provides can in transport and/or discharge process and the method that quickly applies liquid treating agent when not necessarily using mounted production equipment at the volley.Therefore, in some embodiments, the method can in transfer vessel, in manufacture scene or the enforcement of any point place in transfer or discharge process and/or before well site uses.

In some embodiments, the method and is loading, is transporting and implement together with proppant to well site or during well site unloading is used for the process carried after proppant is collected from storage position in bulk.In some embodiments, the method allows processed proppant to keep its free-flowing character to be continuing with the pneumatic handling facilities of routine.In some embodiments, the method can not adversely affect enforcement it uses in conventional fracturing fluid.In some embodiments; the method includes making one or more proppant solids contact with coating composition during one or more such steps, is formed in such step floating coat compositions and control the protective coating that dust is kicked up from the proppant being applied in several seconds of its applying.In some embodiments, producing or except release except reducing dust, this coating provides function benefit for coated proppant.In some embodiments, coating includes or hydrophobic coating.The example that can adopt the additional functionality features that the embodiments described herein increases to proppant includes but not limited to scale inhibition, reduce friction, the coating of tracer-containing, impact modifying agent, the controlled delivery of chemical addition agent, sulfide controls, composite coating, coating is discharged stage by stage with time delay, acidproof and alkaline-resisting coating, corrosion inhibitor, improve the additive of resistance to crushing, suppress the reagent of paraffin or asphaltene precipitation, improve the coating of flow conductivity and for removing the coating of desired anion and halogen from the fluid produced.

In some embodiments, the method includes making fine grained proppant solid (sand of such as given size or ceramic particle) contact with liquid treating agent, and described liquid treating agent comprises following one or more: (a) monosaccharide and/or polysaccharide solution；(b) low-molecular-weight mineral oil；(c) vegetable oil；The mixture of (d) polyethylene and oil；(e)C₆-C₁₆Alcohol alcoxylates；F () polymer and copolymer mixture, it comprises one or more ions and non-ionic acrylate copolymer, acrylate polymer, acrylamide polymer, vinyl acetate polymer, styrene/acrylic/acrylonitrile copolymer；F guar gum that () cross-links；(g) carboxymethyl cellulose；(h) starch；(i) Semen Plantaginis powder；J () is based on the super absorbent polymer of potassium；(k) copolymer；And (I) aforesaid mixture.

The embodiments described herein can be used for other fine particle solid being quickly coated with fracturing sand, pottery, Alumina and using in the similar industrial of fracturing or use gravity-feeder system, belt conveyor and pneumatic conveyor.Method described herein can be used for suppressing airborne dust to be formed, prevent from can adhere to the surface of solids or the existing dust that is entrained in bulk cargo solid becomes airborne, keep sphericity and the integrity of processed solid, maintain the free-flowing character of processed granule while substantially reducing or avoid to produce airborne dust discharge from the solid being transferred, and/or increase functional chemical effect for processed proppant.

The embodiments described herein provides the method for processing free-pouring fine grained proppant solid.In some embodiments, the method includes making solid contact with liquid treating agent less than 5 seconds, and described liquid treating agent has the amount of the liquid treating agent of the free-flowing character being kept substantially processed solid.In some embodiments, described solid contacts with liquid treating agent and each contact procedure was less than 5 seconds more than once.

In some embodiments, described contact includes substantially simultaneously from more than one direction spraying solid.In some embodiments, described solid contacted with liquid treating agent less than 2 seconds.In some embodiments, described solid contacted with liquid treating agent less than 1 second.In some embodiments, described solid contacts the distance elapsed time of 4 feet, solid whereabouts with liquid treating agent.

In some embodiments, liquid treating agent comprises polysaccharide solution.In some embodiments, described liquid treating agent comprises C₆-C₁₆Alcohol alcoxylates.In some embodiments, described liquid treating agent comprises at least one acrylate copolymer.In some embodiments, described liquid treating agent comprises acrylic copolymer.In some embodiments, described liquid treating agent comprises at least one C₆-C₁₆The mixture of alcohol alcoxylates and at least one acrylate copolymer.

In some embodiments, based on the weight of proppant solid, described liquid treating agent is applied to described solid with the Unit Weight amount less than 1wt%.In some embodiments, described liquid treating agent is with the amount less than 0.5wt% and described solid contact.In some embodiments, described liquid treating agent is with the amount less than 0.35wt% and described solid contact.In some embodiments, described liquid treating agent is with the amount less than 0.25wt% and described solid contact.

In some embodiments, described liquid treating agent solid by before static mixer immediately, when or afterwards immediately with described solid contact.

In some embodiments, described contact procedure includes: be applied on described solid by first liquid inorganic agent with the first spray assembly in less than 5 seconds；The solid being processed is made to pass through static mixer；And with the second spray assembly, second liquid inorganic agent is applied on described solid in less than 5 seconds.In some embodiments, described first liquid inorganic agent and described second liquid inorganic agent are different solution.In some embodiments, described second liquid inorganic agent is applied to described solid at described solid immediately by after static mixer.In some embodiments, at least one in described first and second liquid treating agents is effective to being coated with described solid by depositing dust coating.

In some embodiments, at least one in described first and second liquid treating agents is effective to being coated with described solid with additional coatings.In some embodiments, described additional coatings is following one or more: hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise the coating of the ion exchange resin removing anion and/or halogen or its combination in any.

Present invention also offers the free-pouring proppant of coating, it comprises coating that is dry and/or that solidify, and this coating that is dry and/or that solidify comprises the inorganic agent less than about 3wt%.In some embodiments, the free-pouring proppant of described coating compare uncoated proppant present minimizing airborne dust generate.In some embodiments, the free-pouring proppant of described coating comprises the coating of 0.0009-0.5wt%.In some embodiments, the free-pouring proppant of described coating comprises the coating of 0.001-0.35wt%.In some embodiments, described coating comprises following one or more: monosaccharide or the copolymer of polysaccharide, surfactant, alcohol alcoxylates, acrylate copolymer, methacrylate polymer, acrylic acid and/or methacrylic acid, methacrylate and its copolymer, polyvinyl acetate, ethylene acrylic acid co polymer, polybutadiene, low-molecular-weight mineral oil, acrylamide polymer, lignosulfonates, water dispersible natural gum, water-dispersible pectin, water dispersible starch derivant, water-dispersible fiber element derivant, or its any mixture.In some embodiments, described coating comprises one or more monosaccharide or polysaccharide.In some embodiments, described coating comprises one or more alcohol alcoxylates.In some embodiments, described coating comprises at least one C₆-C₁₂Alcohol alcoxylates and at least one C₁₀-C₁₆Alcohol alcoxylates.In some embodiments, described coating comprises one or more acrylate copolymers.In some embodiments, described coating comprises at least one C₆-C₁₂Alcohol alcoxylates, at least one C₁₀-C₁₆Alcohol alcoxylates and at least one acrylate copolymer.In some embodiments, described coating comprises copolymer and one or more methacrylates of one or more methacrylate polymers, one or more acrylic acid and/or methacrylic acid.In some embodiments, described coating comprises following any one or multiple: hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, and/or comprise the coating of the ion exchange resin removing anion and/or halogen, or its any combination.In some embodiments, this coating also comprises sulfide scavanger or antisludging agent.

The brief description of accompanying drawing

Fig. 1 shows the type of equipment described herein and the chart of process flow order.

Fig. 2 illustrates can representational spraying point in the optional static mixer of use as described herein.

Fig. 3 illustrates the representative locations of one group of static mixing rod that the outside of static mixer and spiral be arranged in this static mixer.

Fig. 4 is the view looked down by static mixer, it illustrates the spiral of the static mixing rod being arranged in this blender and arranges.

Fig. 5 illustrates the use of one group of spray nozzle that the periphery around ring positions, and described ring is arranged around the blowpit in proppant handling facilities.

Fig. 6 is the side view of the annular sprayer that figure 5 illustrates.

Fig. 7 illustrates the structure of the tubular static mixer of sprayer assembly and Fig. 3 and 4 being combined with Fig. 5 and 6.

Fig. 8 illustrates alternative constructions, wherein spray figure nozzle at front and static mixer rear.

Fig. 9 illustrates the vertical nonlimiting embodiments processing blender, and it is combined with the partially enclosed upper spraying section above static mixing section, and this static mixing section is presented herein below the lower discharge zone being inwardly tapered.

Figure 10 illustrates the vertical nonlimiting embodiments processing blender, and it is combined with the partially enclosed upper spraying section above static mixing section, and this static mixing section is presented herein below the lower discharge zone being inwardly tapered.

Figure 11 illustrates the vertical nonlimiting embodiments processing blender, and it is combined with the partially enclosed upper spraying section above static mixing section, and this static mixing section is presented herein below the lower discharge zone being inwardly tapered.

Figure 12 illustrates the vertical nonlimiting embodiments processing blender, and it is combined with the partially enclosed upper spraying section above static mixing section, and this static mixing section is presented herein below the lower discharge zone being inwardly tapered.

Explanation

Embodiment disclosed herein provides for processing the fracturing sand whether with cured coating and the method and composition of other fine grained proppant solid (such as the sand of resin coating, Alumina or pottery), it is efficiently used for reducing and processing, load and unload, transport and use, for instance the amount of the airborne dust that such fine grained proppant material is relevant in fracturing.

Embodiment disclosed herein additionally provides and reduces the airborne dust relevant to proppant material self and do not need the method that user, transporter and well site are bought or used extra equipment to load and unload the solid being processed as.

Embodiment disclosed herein provides for by reducing sphericity loss and/or making to comprise the minimized compositions of performance and the method kept or improve proppant solid filling thing of the fine grained that can affect proppant solid performance.

Embodiment disclosed herein provides the method for quickly processing proppant, and described method is minimum on the impact being currently used for loading, move and unloading that be coated with or uncoated proppant sand or pottery conventional dock technology and equipment.

Embodiment disclosed herein includes but not limited to liquid treating agent rapidly and at the free-pouring proppant solid of the of a sufficiently low free-flowing character to maintain processed solid used and process under ratio.Without wishing to limited to any particular theory, such low-level ground uses the process of reagent to make the solid being processed that conventional dock equipment can be used to load and unload, without negatively affecting handling and transportation.Inorganic agent can also help avoid the degraded of proppant solid or rotten.Some beyond thought advantages of method and composition described herein include but not limited to that protection sphericity and the resistance to crusing benefit relevant to proppant avoid the formation of fine powder (such as dust) simultaneously, and described fine powder can be changed into airborne health hazard or is in the high concentration of the performance being enough to affect fracturing fluid.The embodiments described herein may be additionally used for the proppant oily gentle well operations having extra function and/or value benefit by adding functional molecules to provide in coating.

Advantage and the further advantage of the embodiment described in full will be apparent from for those skilled in the art.Additionally, some advantage of the embodiments described herein includes but not limited to that protection proppant particles can also help to reduce transporting described sand to be transported to the abrasion of the pneumatic lorry in well site from the method worn and torn in handling or pneumatic conveying process.Therefore, the embodiments described herein not only contributes to controlling airborne dust, but also limits in the abrasion moving and loading and unloading pipeline and the accessory used in described solid.Embodiment described herein can also effectively reduce the discharge end of high-pressure pump is connected to the pressure piping of well head and the abrasion of accessory.Such as, owing to a large amount of proppants are pumped, pressure piping and accessory must test the impact determining proppant abrasion to its intensity often.The embodiments described herein can help reduce the abrasion to equipment and thus extend its service life.

Control can pass through method described herein and process realization from the airborne dust of fracturing sand and other proppant.In some embodiments, described process includes making fine grained proppant solid contact with liquid treating agent, the amount of described liquid treating agent is enough to suppress airborne dust from processed solid discharge and/or to give extra functional chemical benefit, still maintain the free-flowing character of processed solid simultaneously, such as proppant before treatment those, it is possible to utilize gravity charging, pneumatic and belt conveyor handling system with remaining valid.In some embodiments, process is occurred in 10 seconds or less time and carries out when solid free-falling, directed ground free-falling (as fallen by static mixer) or in process of pneumatic transmission.During these times, the free-flowing character of solid makes them be especially susceptible to contact with one or more scattered liquid spray agent and turbulent closure scheme.

Even if making solid can moisten the amount that required amount is less with perceiving with ratio, when namely processing with the amount less than 0.7wt% moisture to keep free-flowing character, or when processing with the amount of 0.05-0.4wt% in some embodiments, impacting due to discharging and be quickly completed, what dust emission was also significantly reduced and was ejected is microgranule.Such performance makes the proppant being processed continue with existing handling facilities as effectively loaded and unloaded based on the discharge system of gravity, mobile belt, pneumatic conveyer system etc..

The solid that can be processed is and keeps to be the fine grain free-pouring solid of the size being generally of about 0.2 millimeter to about 1 millimeter.Such solids size is used for strutting the crackle that down-hole is formed in the stratum of fracture in fracturing.Such crackle supporter (crackprops) or " proppant " as known in them must resist the crushing force of crack closure to help to maintain the flowing of the liquids and gases in the earth formation of trap.It is commonly used for that the material of proppant includes coating and uncoated sand, Alumina and ceramic proppant material.All such materials all use suitable in the method being described herein as and process.

In embodiments more described herein, embodiment uses liquid treating agent, this liquid treating agent applies with extremely low level, such as, avoiding making the level of microgranule discernable ground moistening, the moistening of described discernable ground such as, by such as drop, the puddles of water, visual moistening gloss or " sensation " moistening when the solid that handling are processed.In some embodiments, some process be likely to need after contacting with the inorganic agent of spraying slightly dry, to avoid the granule of " moistening of discernable ground ", those preparation especially with non-water solvents carrier.

In some embodiments, the level of inorganic agent also volume that is quick and that apply is sufficiently small, to avoid the formation of by conventional drying proppant solid handling facilities, for instance the firm caking of the processed solid that gravity feeding conveying system, pneumatic transportation etc. can not easily be transported.In other words, the proppant solid that the method according to the invention processes continues to function and experiences the handling of conventional proppants solid handling facilities and system.In some embodiments, liquid treating agent be applied to solid or with solid contact less equal than 20,19,18,17,16,15,14,13,12,11,10,9,8,7,6,5,4,3,2 or 1 seconds.As used herein, unless expressly stated, otherwise when relating to certain period of time and using, the phrase of use " less than " do not include zero.In some embodiments, liquid treating agent and solid contact about 0.1 were to about 5 seconds, about 0.1 to about 10 second, about 0.1 to about 15 second or about 0.1 to about 20 second.In some embodiments, liquid treating agent and solid contact about 1 to about 10, about 1 to about 9, about 1 to about 8, about 1 to about 7, about 1 to about 6, about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1 to about 2 seconds.In some embodiments, liquid treating agent and solid contact about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, about 0.5 to about 5, about 0.5 to about 4, about 0.5 to about 3, about 0.5 to about 2 or about 0.5 to about 1 seconds.In some embodiments, liquid treating agent and solid contact about 2 to about 10, about 2 to about 9, about 2 to about 8, about 2 to about 7, about 2 to about 6, about 2 to about 5, about 2 to about 4 or about 2 to about 3 seconds.In some embodiments, liquid treating agent and solid contact about 3 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 to about 6, about 3 to about 5 or about 3 to about 4 seconds.In some embodiments, liquid treating agent and solid contact about 4 to about 10, about 4 to about 9, about 4 to about 8, about 4 to about 7, about 4 to about 6 or about 4 to about 5 seconds.Time period described herein can combine with any embodiment relating to the process that solid contacts with liquid treating agent described herein and use.Phrase " time period as described herein " refers to except with regard to these periods except any particular specifically described any period.

In some embodiments, liquid treating agent exists with aqueous solution, dispersion or emulsion form.In some embodiments, the level of suitable liquid inorganic agent can be characterized as being the weight of the solid that the processed solid of per unit weight applies.In some embodiments, according to such referential, liquid treating agent suitable uses processed solid (such as sand) that ratio the is per unit weight inorganic agent solid less than 5wt%.In some embodiments, liquid treating agent applies with the ratio less than about 3wt% and can not adversely affect the free-flowing character of processed proppant after the material applied is dried.In some embodiments, inorganic agent applies with the amount of about 0.0002 to about 1.5wt%, about 0.0002 to about 1wt%, about 0.0005 to about 0.85wt%, about 0.0007 to about 0.75wt%, about 0.0008 to about 0.65wt%, about 0.0009 to about 0.5wt%, about 0.001 to about 0.35wt% and about 0.0013 to about 0.25wt%.In some embodiments, the liquid treating agent that amount is proppant solid about 3 per ton to about 8 pounds of liquid treating agent.In some embodiments, solid can be used ratio with the business under the speed of about 400 ton hour, to depend on device therefor and contacts with liquid treating agent.In some embodiments, the inorganic agent of about 3 to about 8 pounds is based on the dispersion with about 40% solid.

As described herein, solid quickly contacts with liquid treating agent, so that this process is prone to load and unload in loading, transporting or quickly process at the volley when unloading operation.As herein described, solid can contact the short time period with inorganic agent, the described short time period includes but not limited to less than 5 seconds but time period more than 0.In some embodiments, the described time period is about 1 to about 3 second.In some embodiments, described solid contacts in solid whereabouts 3-4 foot (1-1.3 rice) elapsed time with liquid treating agent.In some embodiments, spraying dispersing nozzle is used to make liquid treating agent and described solid contact.In some embodiments, liquid treating agent and described solid contact is made by multiple spraying dispersing nozzles, the proppant flow of described spraying dispersing nozzle collision whereabouts or directed whereabouts, or when described solid be pneumatic conveying load or unload time, liquid treating agent is incorporated on proppant solid by described spraying dispersing nozzle.

Liquid treating agent can with any such mode and solid contact, and described mode reasonably effectively provides the dispersion of substantially homogeneous liquid treating agent on solid as much as possible in treatment region to solid.Described method can such as depend on existing equipment, budget and space.In some embodiments, described contact arrangement is the paint finishing with at least one nozzle, described nozzle processed solids movement through and by treatment region on processed solid, under, distribute liquid treating agent about and within.In some embodiments, there is multiple nozzle.

In some embodiments, when proppant is unloaded from haulage vehicle and passes through Belt Conveying to discharge apparatus, the position of typical treatment region can set along conveyer belt.In some embodiments, treatment region includes 1 to 8 nozzle and/or Atomizing Spray Nozzle, with formed from contact with the proppant of movement above and below conveyer belt or when solid falls from conveyer belt carefully spray, mist or smog, to realize substantially uniform process.

In some embodiments, treatment region can to hold inorganic agent when applying described treatment additive in the shell around this induction system/conveyer belt setting position better, to better control over the environment applying point around, or so that contact process is more efficient.

Proppant solid can also be heated immediately before or after contact procedure or allow to be heated to the temperature of rising, namely more than 25 DEG C or at the temperature of about 30 DEG C to about 85 DEG C such that it is able to the liquid treating agent applying higher concentration maybe can adopt less expensive additive to strengthen performance.

In some embodiments, another treatment region may be located in air conveyer or combines with air conveyer.One or more spray nozzles (such as thin spray nozzle) can align and orientation is to be discharged into liquid treating agent in pneumatic flow with suitable injection rate in one or more positions, thus liquid treating agent with when being transferred solids mixing and move in traffic flow with the solid contact being transferred.

In some embodiments, treatment region is arranged in one or more reloading points of cargo handling process, is move and be easily achieved to be sufficiently mixed at reloading point place solid.In some embodiments, they mix with static mixer to strengthen the mixing of processed solid and to promote liquid treating agent substantially homogeneous distribution on solid.In some embodiments, position includes delivering the proppant solid being stored to be transported to the loading ports of van, for loading the port of discharge of pneumatic transportation lorry, and when lorry well site unload proppant time unload material strip.In some embodiments, the method includes being applied on solid by first liquid inorganic agent with the first spray assembly within the time period as described herein；The solid being processed is made to pass through static mixer；And with the second spray assembly, second liquid inorganic agent is applied on described solid within the time period as described herein.In some embodiments, described first liquid inorganic agent and described second liquid inorganic agent are different solution.In some embodiments, described second liquid inorganic agent is applied to described solid at solid immediately by after static mixer.In some embodiments, at least one in described first and second liquid treating agents is coated with described solid with depositing dust coating effectively.In some embodiments, at least one in described first and second liquid treating agents is coated with described solid with additional coatings effectively.In some embodiments, described additional coatings be hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise the coating of the ion exchange resin removing anion and/or halogen.Such coating has description in this article, but also can apply other coating.

In some embodiments, liquid treating agent is at the position of reloading point and proppant solid contact and mixes, and the position proppant solid at reloading point is discharged and the free-falling of experiencing some periods is to vertical lower section point.Such position allows to use one or more spray nozzles.Such as, in 1 to 3 grade can by circular pattern around fall solid as arranged 1 to 12 nozzle around discharge gate.In some embodiments, multiple nozzle is used.In some embodiments, multiple nozzle, each nozzle is used to have alignment and aim to spray liquid treating agent to the solid fallen and be coated with sector or the conical jet pattern of described solid.In some embodiments, before by static mixer, in process and/or described contact occurs afterwards immediately, described static mixer utilizes the momentum of the falling solids better mixing and distribution to promote liquid treating agent on described solid.

As directed, heat insulation and/or heating shell (1) protection water tank (2) and liquid treating agent concentrate storage element (3), (4), (5), (6) are from the impact of the great variety of ambient temperature.Pump (7) is for moving to liquid treating agent blender (9) from holding vessel (2) by filter (8) by water.Liquid treating agent is delivered to blender (9) from storage element (3-5) with the controlled rate expecting concentration rate being sufficient for being used in disclosure method by pump (10), or is delivered to top and the front place of next-door neighbour's blender (9).Pump (11) is used to the liquid treating agent (12) of dilution is transferred to blender (13) and disperses with the speed within the scope of such as 1.7-5 gallon per minute under 40-60psi with one or more spray nozzles (14) during motion under the sand processed is with the typical commercial volume of such as 100-400 ton hour.Proppant sand (15) is delivered to the top of blender (13), this blender is suitable for static mixer, the sand being sized to process commercial volumes of this static mixer, the liquid treating agent that wherein proppant sand (15) sends with the first spray assembly from spray nozzle (14) mixes.

If valve (17) cuts out, recirculation circuit (16) can be used for keeping liquid treating agent to move in pipeline.

Optional air compressor (18) can be used for providing pressurized air source to shell (1) and/or blender (13).Optional power generator (19) serves as shell (1), including pump (7), (10), (11), and the source of the non-firm power of blender (9).

Illustrate in detail blender (13) in fig. 2 to a certain extent, such as static sand blender.In the figure, liquid treating agent (12) is by the nozzle (14) of the sand entrance (20) around blender (13), and in blender (13), liquid treating agent (12) contacts with sand (21) when sand (21) is by Tu She district (22).Sand (21) contacts a series of mounted collision type bar or the hybrid component (23) of the whole vertical height setting position along Mixed Zone (24) subsequently.In some embodiments, hybrid component (23) is circular, avette, arc, slope shape, triangle, foursquare (being suitably set to there is the edge pointed up) or rhombus, or the shape of cross section being otherwise selected as presenting is for redirecting it or directed when each particles fall of sand (21) is by mixed zone (24), thus realizing hybrid motion.By clashing into and deviate the side of circular hybrid component (23), the liquid treating agent (12) on sand (21) is re-distributed thus being more uniformly distributed liquid treating agent in a substantially uniform manner in the main body of sand (21).Illustrate that use has enough material hardnesses to resist pipeline or the bar of the abrasive action of the sand of whereabouts, to help when component (23) weares and teares to build and safeguard.

In some embodiments, hybrid component (23) by suitable securing member or support by detachably connected, be fixed or maintained in blender (13) so that component (23) is maintained in blender (13), regardless of by the friction of the sand of its whereabouts and power.Suitable securing member may include but be not limited to enter the bolt in this component (23) in the horizontal direction, component (23) is fixed to the horizontal bolt of the blender (13) of one or more flanges with the sidewall self fixing, weld or being connected to blender (13) or support, or component (23) is fixed on the maintenance support (not shown) of U-shaped therein or L-shaped through vertical motion.

In some embodiments of blender (13), there is transition region (25), it makes the sand being processed stop before passing through to export (26) discharge.Such transition region is for reducing the momentum of the sand being discharged and thus limiting the power that can eject airborne dust when the processed sand fallen deposits.

The acceptable alternative type of static mixer (13) shows in figures 3 and 4.Described static mixer generally cylindrical (as the bucket of 55 gallons, wherein the diameter of top entry (27) is of substantially equal with the diameter of outlet at bottom (28)) and be sized to receive, mix and discharge the proppant sand of large volume.In the present embodiment, static collision type hybrid component (23) is formed by a series of bars or pipe (29), described bar or manage (29) flatly across bucket (30) and helically pattern (31) be vertically distributed along the height of bucket (30) with span (32).The lower section of the discharge gate that three eyelets (33) are the free-falling that blender is suspended on conventional proppants sand handling facilities being connected to the top of this bucket (30) provides supporting.

Fig. 5 and 6 illustrate spray assembly (34), and it can use with tectonic association as in fig. 7 with the static mixer (13) of Fig. 3 and 4.More specifically, spray assembly (34) is connected for one group of spray nozzle (14) that 3-7 is individual around the girth of sand outlet suitably with one or more, and described spray nozzle (14) is substantially homogeneously distributed around described spray assembly (34).Each nozzle (14) orientation inwardly and downwardly diametrically, there is the spray pattern region (36) of overlap, so that be introduced into the sand of top entry (27) with by the top of static mixer (13) or one or more liquid treating agents spray jet hit that the nozzle (14) that is close in static mixer (13) front sends, the position of this static mixer (13) is close to the lower section of ejection assemblies (34) to discharge processed sand (35).Connector or belt (37) on spray assembly (34) are scattered in the lower section so that this static mixer to be suspended on this spray assembly that cooperates with the eye hook (33) on static mixer.

Fig. 8 illustrates the replacement scheme of the blender shown in Fig. 7, merely add the second spray assembly (38), this second spray assembly is connected to second liquid inorganic agent (39), and second liquid inorganic agent (39) can be identical or different with liquid treating agent (12).Exemplary second liquid inorganic agent comprises the steps that the dust Control agent and above-mentioned function treatment that introduce as first liquid inorganic agent (12).Second spraying area can be used for increasing by the second function for coating or only assisting in ensuring that and cover more proppant's surface area by coating procedure.Second nozzle (40) is oriented at Jet with downward flow direction second liquid inorganic agent (39) when discharging processed sand (41).

Fig. 9-12 further illustrates the replacement scheme of the contact device of the dust Control liquid treating agent for spraying, the dust Control liquid treating agent of injection proppant solid contact when solid directed free-falling under gravity and in motion.Considering the use of online jet spread system, itself and the Conventional pneumatic transportation system coupling somewhat reequiped to provide dust Control to process when proppant solid is transported to storage place or transports from storage.

As shown in Fig. 9-12, contact mixer (42) be portrait orientation to allow proppant solid to be fallen by it.Top (43) has the vertical lip (44) of the reinforcement of the introducing opening (45) around cap (55).The diameter on this top (43) is more than the diameter of opening (45), so that dust Control liquid treating agent is inwardly distributed to the whereabouts stream of pending proppant from comparatively safe peripheral position by nozzle (14), this peripheral position is not subjected to the impact of efflux of solids and the associated abrasion fallen.

As shown in the figure, supply interface (47) is connected to the circular manifold (48) that the nozzle (14) inwardly directed with the center towards device is in fluid communication, in order to supply liquid treating agent to proppant under stress when proppant is fallen by opening (45).The upper horizontal surface (49) of cap (55) extends internally to provide the part upper cover of contact area towards lip (44), it also reduces the airborne dust risen during processing procedure.The sidewall of the convergent inwardly of nozzle (14) lower section contributes to guiding solid into middle mixing unit from sidewall.

Handle (50) can be fixed to the outside of the sidewall of (43) topmost such as 2-4 handle and/or hanger (51) such as 2-4 hanger, to handle and to position this device.

The external shape of the mid portion (52) of contact mixer (42) can be columnar and can include multiple static mixing ways (53).As directed, static mixing ways (53) can be configured to the multiple spoke members in outer shroud (56), as modular, substantially flat, comprise the ring element (54) of spoke.Figure 10 illustrates five such ring elements (54) with spoke of use, each have six guiding spoke members (55), they around ring (56) inner homogeneous be distributed and they at the substantially geometric center place of respective ring element (54) intersect.Mixing ways (53) can be fixed to outer shroud (56) by any method, and described method includes melting welding, soldering, brazing and/or securing member (faster).Each guide ring component (54) can be fixed to ring (56) by melting welding, brazing, soldering or similar permanent and durability connected mode.

Then by each ring element (54) vertical stacking and stagger appropriate angle to provide ways (53) along the downward spiral traveling of the length of mid portion (52) blender (46) in relative to previous ring element (54) successively in the mid portion (52) of bottom part (57) top.Nethermost ring element (54) can be located at the top of bottom part (57), but can be fixed to support lug or the supporting of support (not shown) of medial wall by the bottom (61) in mid portion (52).

The module nature of the mixing arrangement of this form allows to adjust mixability and incorporation time based on the quantity of the quantity mixing spoke existed in each cell and the mixing module used in the apparatus.

The bottom part (57) of blender (46) can be straight tube form (namely relative to the outside of mid portion (52) into about 180 °), but can be shown as the frustoconical cross-sectional (60) being inwardly tapered that angle (58) is within the scope of about 150-175 ° or angle is within the scope of about 160-170 °.This tapered cross-section contributes to the microgranule guiding and being deposited on the periphery of the proppant flow of process to discharge from bottom opening (59).Similarly, the bottom of tip portion (43) can present with the vertical direction angle (62) into about 15-45 ° or 25-35 ° convergent inwardly.

Therefore, in some embodiments, it is provided that for the method processing free-pouring fine grained proppant solid.In some embodiments, the method includes making solid contact less than 5 seconds with liquid treating agent, the amount of the liquid treating agent that amount is the free-flowing character being kept substantially processed solid of described liquid treating agent.Described liquid treating agent can be any reagent described herein and comprise one or more compositionss described herein.In some embodiments, described solid contacts more than once with liquid treating agent and each contact procedure was less than 5 seconds.Time period for contacting can also is that any time section described herein.

Method described herein is suitable to apply to multiple fine grained proppant solid coating or reagent.Example includes but not limited to uncoated sand, have and solidify or the partially cured sand of coating, Alumina, pottery, the Alumina of coating or pottery.In some embodiments, described fine grained proppant solid is uncoated sand or the sand through resin coating.

In some embodiments, described method includes in solid free-falling, directed free-falling or is sprayed on proppant solid by liquid treating agent in pneumatic conveying process.Other embodiment described herein can also be the part of the method.Described solid substantially simultaneously can also be sprayed from more than one direction.

As described herein, method described herein can be used for applying depositing dust coating.This liquid treating agent can also is that being coated with described solids with following one or more effective or for being coated with described solids with following one or more: hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, and/or comprise the coating of the ion exchange resin removing anion and/or halogen, or its combination in any.The example of such coating is described in herein.

In some embodiments, it is provided that a kind of method for producing the free-pouring fine grained proppant solid with depositing dust performance.In some embodiments, the method includes making described solid contact the time period described herein with depositing dust liquid treating agent, and the amount of described depositing dust liquid treating agent is kept substantially the free-flowing character of processed solid and reduces the dust produced by solid.In some embodiments, the free-pouring fine grained proppant solid with depositing dust performance the dust produced is less than the dust produced by the solid not contacted with depositing dust liquid treating agent.In some embodiments, depositing dust liquid treating agent with hydrophobic coating, reduce friction coating, comprise the coating of tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, the coating suppressing asphaltene precipitation and/or the coating that comprises the ion exchange resin removing anion and/or halogen to be effectively coated with described solid.That is, in some embodiments, described coating can have the function of more than one.In some embodiments, depositing dust inorganic agent comprises polysaccharide solution.In some embodiments, described depositing dust inorganic agent comprises C₆-C₁₆Alcohol alcoxylates.In some embodiments, described depositing dust inorganic agent comprises at least one acrylate copolymer.In some embodiments, described depositing dust inorganic agent comprises acrylic copolymer.In some embodiments, described depositing dust inorganic agent comprises at least one C₆-C₁₆The mixture of alcohol alcoxylates and at least one acrylate copolymer.In some embodiments, based on the weight of described proppant solid, the amount being applied to the depositing dust inorganic agent of described solid is the unit weight amount less than 1wt%.In some embodiments, described amount is the amount less than 0.5wt%.In some embodiments, described amount is the amount less than 0.35wt%.In some embodiments, described amount is the amount less than 0.25wt%.

In some embodiments, described depositing dust inorganic agent comprises C ethoxylation, propenoxylated₆-C₁₂Alcohol, C ethoxylation, propenoxylated₁₀-C₁₆The emulsion of alcohol, acrylate copolymer and water.In some embodiments, described depositing dust inorganic agent comprises surfactant.In some embodiments, described depositing dust inorganic agent comprises the ammonia less than 0.1%.In some embodiments, described depositing dust inorganic agent comprises free (the such as remnants') monomer less than 0.05%.In some embodiments, dust disposal agent comprise about 15% to about 30%, about 17% to about 28% or about 20% to about 25% ethoxylation, propenoxylated C₆-C₁₂Alcohol.In some embodiments, dust disposal agent comprise about 5% to about 20%, about 8% to about 18% or about 10% to about 15% ethoxylation, propenoxylated C₁₀-C₁₆Alcohol.In some embodiments, depositing dust reagent comprises the C ethoxylation of about 20% to about 25%, propenoxylated₆-C₁₂Alcohol, the C ethoxylation of about 10% to about 15%, propenoxylated₁₀-C₁₆Alcohol, the acrylate copolymer of about 5% to about 10%, the ammonia less than 0.1%, the Free Monomer less than 0.05%.In some embodiments, depositing dust reagent comprises the C ethoxylation of about 20% to about 25%, propenoxylated₆-C₁₂Alcohol, the C ethoxylation of about 10% to about 15%, propenoxylated₁₀-C₁₆Alcohol, the acrylate copolymer of about 5% to about 10%, the ammonia less than 0.1%, the Free Monomer less than 0.05%, remaining for water.

In some embodiments, it is provided that a kind of method for being coated with free-pouring proppant.In some embodiments, the method includes making described proppant contact the time period described herein with liquid treating agent, the amount of described liquid treating agent is that the free-flowing character being kept substantially proppant is to produce the free-pouring proppant of coating, wherein said coating is depositing dust coating, hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, and/or comprise the coating of the ion exchange resin removing anion and/or halogen, or its combination in any.In some embodiments, described coating is depositing dust coating.In some embodiments, described coating be hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise coating or its combination in any of the ion exchange resin removing anion and/or halogen.

Additionally providing the free-pouring proppant of coating, it comprises coating that is dry and/or that solidify, and coating that is described dry and/or that solidify comprises the liquid treating agent less than about 3wt%.In some embodiments, the free-pouring proppant of described coating presents airborne dust generation minimizing compared with uncoated proppant.In some embodiments, the free-flow proppant of described coating comprises the coating of 0.0009-0.5wt%.In some embodiments, the free-flow proppant of described coating comprises the coating of 0.001-0.35wt%.In some embodiments, described coating comprise following in one or more: monosaccharide or polysaccharide, surfactant, alcohol alcoxylates, acrylate copolymer, methacrylate polymer, acrylic acid and/or methacrylic acid copolymer, methacrylate and its copolymer, polyvinyl acetate, ethylene acrylic acid co polymer, polybutadiene, low-molecular-weight mineral oil, acrylamide polymer, lignosulfonates, water dispersible natural gum, water-dispersible pectin, water dispersible starch derivant, water-dispersible fiber element derivant or its any mixture.

In some embodiments, described coating comprises one or more monosaccharide or polysaccharide.In some embodiments, described coating comprises one or more alcohol alcoxylates.In some embodiments, described coating comprises at least one C₆-C₁₂Alcohol alcoxylates and at least one C₁₀-C₁₆Alcohol alcoxylates.In some embodiments, described coating comprises one or more acrylate copolymers.In some embodiments, described coating comprises at least one C₆-C₁₂Alcohol alcoxylates, at least one C₁₀-C₁₆Alcohol alcoxylates and at least one acrylate copolymer.In some embodiments, described coating comprises one or more methacrylate polymers, one or more acrylic acid and/or methacrylic acid copolymer and one or more methacrylates.In some embodiments, described coating be hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise the coating of the ion exchange resin removing anion and/or halogen.In some embodiments, described coating also comprises sulfide scavanger or antisludging agent.

This document describes multiple different liquid treating agent.According to any one in various embodiments described herein, described liquid treating agent can be applied to solid.Described liquid treating agent can simultaneously or sequentially apply.Additionally, method described herein can be used for increasing multiple layers or coating for described solid.Described liquid treating agent also can individually apply or apply with combination in any to each other.Illustrating on the contrary unless clear and definite, otherwise the method is not limited to apply any coating.

The liquid treating agent that can use in process described herein can be aqueous solution or emulsion.In some embodiments, described liquid treating agent can be used for reducing the dust produced by solid.This is referred to alternatively as " dust controlling ".In some embodiments, can be such as aqueous solution or emulsion for controlling the liquid treating agent of dust, it comprises one or more polysaccharide, surfactant and alcohol alcoxylates, acrylate copolymer, methacrylate polymer, with acrylic acid and/or the copolymer of methacrylic acid, polyvinyl acetate, ethylene acrylic acid co polymer, methacrylate (referring to U.S. Patent No. US4,594, No. 268) and containing the copolymer of methacrylate, polybutadiene, low-molecular-weight mineral oil and its mixture.Use aqueous solution that liquid treating agent can be bought as concentrate and afterwards when needed or at acquisition dilution water for being at once diluted to working concentration.Aqueous based dispersions is used to also avoid the needs loading and unloading another hydrocarbon material in well site.

Suitable monosaccharide and polysaccharide include starch, sugar and the material based on sugar.The example of such material includes but not limited to molasses, glycerol, blackstrap, blackstrap molass, syrup residue, mother solution, bagasse, sugar grass molasses, timber molasses or Semen Maydis molasses and/or the Radix Betae or the sucrose syrup that are formed in the original preparation or refining process of sugar.For example, with reference at the soil fertility quality described in WO2013/029140, it carries out with (a) residual liquid and (b) sugary soln.Residual liquid (a) originates from the aqueous solution effluent (such as syrup or solution) (remaining or be not) of sweat.Residual liquid (a) is the aqueous solution including at least citric acid, inorganic matter (such as mineral), protein material and glucide.Described sugar comprise selected from fructose, glucose, maltose carbohydrate and/or selected from the polyhydric alcohol of arabitol, erythritol or its mixture.Still referring to U.S. Patent No. No. 6,790,245 and No. US7,157,021.

Available surfactant and the not limiting example of alcohol alcoxylates include but not limited to C₁₀-C₁₄Alpha-alkene sulfonate, C₁₀-C₁₆Alcohol sulfate, C₂-C₁₆Ether alcohol sulfate, C₂-C₁₆α-thioesters, highly branched anion surfactant, as the molecular weight block copolymer less than 600 and derived from the nonionic surfactant of ethylene oxide/propylene oxide or other epoxide, as the C with every mol of alcohol four to ten moles of ethylene oxide ethoxylation₈-C₁₆The nonionic surfactant of branched-chain alcoho, and mixture.Process for example, with reference at the coal dust described in Canadian Patent No. 2,163,972 and U.S. Patent No. 4,592,931.Referring further to U.S. Patent No. 6,372,842,5,194,174,4,417,992 and 4,801,635.Other example includes in those described in EP01234106A2, U.S. Patent No. 3,900,611, U.S. Patent No. 3,763,072, WO2005/121272 and US publication application the 2007/073590th.Any overlap on molecular length in above-mentioned scope is attributed to the practical situation of commodity production and separation and those skilled in the art will so recognize.

Various water solublity or aqueous dispersion polymers or polymer emulsion can also be parts for liquid treating agent.Example includes but not limited to acrylate copolymer and copolymer, methacrylate polymer and the copolymer of acrylic acid and/or methacrylic acid.The example of spendable alcohol alcoxylates includes but not limited to acrylic acid and one or more unsaturated aliphatic carboxylic acids, or can with the acrylic copolymer of the unsaturated compound of acrylic acid copolymer, described unsaturated aliphatic carboxylic acid such as 2-chloracrylic acid, the acid of 2-bromopropene, maleic acid, fumaric acid, itaconic acid, methacrylic acid, mesaconic acid etc., described can with the unsaturated compound of acrylic acid copolymer such as acrylonitrile, acrylic acid methyl ester., methyl methacrylate, vinyl acetate, propionate, itaconic acid methyl ester, styrene, 2-hydroxyethyl methacrylate etc..

In some embodiments, the weight average molecular weight of described polyacrylic acid or acrylic copolymer is about 5,000 to about 30000000 or from about 1000000 to about 5000000.In some embodiments, the amount of acrylate copolymer existed in the mixture containing polyprotic acid is that every parts by weight of polyol acid about 2 is to about 50, about 3 to about 10 or about 4 weight portion.Referring to U.S. Patent No. 4,592,931, the disclosure of which is incorporated herein by reference.

Polyvinyl acetate and ethylene, propylene acid solution and emulsion can be also used in liquid treating agent.Such as, water-dispersible acrylic and ethene polymers are applicable, include but not limited to acrylic acid, vinyl alcohol, vinyl acetate, dimethyl diallyl ammonium chloride (DMDAAC), acrylamido propyl sulfonic acid ester (acrylaminylpropylsulfonate, etc. AMPS) homopolymer, copolymer and ter-polymers, and combination.

Acrylamide polymer can be also used in liquid treating agent.The example of acrylamide polymer includes but not limited to that about the 0.5 of gained mixture to the polyacrylamide copolymer of the amount of about 20wt%.In some embodiments, described acrylamide adds with the amount of about 1 to about 2wt%.The example of suitable acrylamide includes but not limited to charged PAMA or polyacrylamide polyacrylate copolymer, and its mean molecule quantity is 3000000 to 25000000g/mol and charge density is 10% to 60%.The not limiting example of the acrylamide product being purchased includes: the AN934XD from SNF, Inc., the AF306 from Hychem, Inc., and the Magnafloc336 from CIBA.

Polyacrylamide can be used alone or with the starch coupling of the modified dissolubility to strengthen in cold water.Referring to the U.S. Patent Publication application the 20130184381st of U.S. Patent No. 5,242,248 (processing for the arenic polyacrylamide of horse racing) and announcement, the disclosure of which is incorporated herein by reference.

Lignosulfonates also serve as liquid treating agent or are used as the component of liquid treating agent.Example includes but not limited to lignosulfonates such as ammonium lignosulphonate and the alkali and alkaline earth metal ions salt of lignin sulfonic acid, such as sodium lignin sulfonate, calcium lignosulfonate etc., and combination.In some embodiments, ammonium lignosulphonate can be used.Limit without wishing to by any particular theory, ammonium lignosulphonate can be used to avoid adding inorganic material, such as calcium and sodium, especially sodium.

Described liquid treating agent also can comprise one or more water dispersible natural gums, water-dispersible pectin, water dispersible starch derivant or water-dispersible fiber element derivant.The example of natural gum includes: terrestrial plant secretions, and it includes but not limited to Radix Acaciae senegalis (arabic gum, acacia), Tragacanth, POLY-karaya etc.；Terrestrial plant seed viscose glue, it includes but not limited to plantasan, Semen Lini glue, guar gum, tracasol, tamarind ready-mix powder, Flos abelmoschi manihot etc.；Derivative thalassophyte viscose glue, it includes but not limited to algin, alginate, carrageenin, agar, Furcellaran etc.；Other terrestrial plant extract, it includes but not limited to arabinogalactan, pectin etc.；Fermentable product, it includes but not limited to xanthan gum, dextran, scleroglucan etc..Cellulose derivative includes cellulosic chemical derivative, includes but not limited to the ethers of alkyl, carboxyalkyl, hydroxyalkyl and combination and sulphonic acid ester and phosphate ester.

In some embodiments, described guar gum is solution, and its viscosity scalable is to adapt to the change of solid being processed.Such as, the viscosity of guar gum solution can be processed by gamma ray to regulate and apply at temperature the viscosity of about 40 to about 140cps under 1% concentration to obtain.Guar gum (as by Rantec, Inc. with trade name SuperTack, C7000, J3000 and HVX sell those)；Carboxymethyl guar locust beam gum (CMGuar as sold by MaharashtraTraders)；Carboxymethyl Semen Cassiae powder (CMCassia as sold by MaharashtraTraders)；Carboxymethyl cellulose (FinnFix300 as sold by Noviant)；Starch (Semen Maydis (corn), Semen Maydis (maize), Rhizoma Solani tuber osi, Maninot esculenta crantz. and wet method grind/GW8900 that sells of the starch such as KTMIndustries of spray drying)；Starch with cross-linking agent such as epoxychloropropane and phosphorus oxychloride pretreatment；Carboxymethyl starch (substitution value (DS) of 0.2 to 0.3, such as the AquaBloc sold by ProcessProductsN.W., KogumHS, RT3063 and RT3064)；Hydroxypropylguar；Hydroxyethylguar；Carboxymethyl-hydroxypropylguar；Hydroxyethyl starch；Oxytarch；And hydroxyethyl cellulose.Other example of polymer includes Semen Cassiae powder, Cillium, xanthan gum, any cereal-granules, the polysaccharide (Daubentonia, Robinia pseudoacacia L., locust beam gum, Semen Lini and POLY-karaya) that obtained by the seed of annual or perennial dicotyledon.

In some embodiments, before adding guar gum, water cross-linkable agent for inorganic agent preparation processes with the ratio of every 100 parts of polymer 30-50 part cross-linking agent, described cross-linking agent is prepared (such as, with the trade (brand) name TYZOR217 DuPont product sold) by the blend of a Biformyl and two parts of zirconium lactates.Such as, for the water of 15 gallons (125.1-pound), the guar gum of 1.75-pound dosage is added；The cross-linking agent (the 40% of the polymer of 1.75-pound) of 0.70-pound dosage was added before adding polymer.In some embodiments, guar gum polymer can by weight 0.70% to 1.4% ratio add in water.Plasticizer, glycerol can also be added in the ratio of the 0.5 to 5% of guar gum solution weighing scale.

Water dispersible starch derivant includes but not limited to the alkyl of starch, carboxyalkyl, hydroxyalkyl and the combination ether prepared by various different chemistry or enzyme reaction method；The phosphate ester of starch or sulphonic acid ester etc..

Table 1 and 2 is the indefiniteness sample list that can be used for processing the proppant solid kind for liquid, the suppression dust chemical liquid treatment agent of dust controlling and trade name according to technique described herein and method.

Table 1

Table 2

Product described herein can with solid contact described herein.The method is not limited to specific embodiment.Typical commercial is available and is described as can be used for controlling not paving road dust, the liquid treating agent suppressing dust from other liquid of stock pile and the dust of similar structures can also be used.Such reagent can be aqueous or based on solvent, but is not only water or volatile solvent.Namely in some embodiments, liquid treating agent is not free from water or the volatile solvent of other component any.The list of such material has been announced by Albuquerque city and can find in goo " dot " gl/wlehmI.

In some embodiments, liquid treating agent can be the form of the shallow layer that can be solidified by water or contact with moisture with environment, for instance the alkyd resin that can solidify upon exposure to moisture.

In some embodiments, liquid treating agent comprises light mineral oil, and it can with light oil form or aqueous form and the proppant solid contact with surfactant.Can be used as the mineral oil that the mineral oil of liquid treating agent/can be used in liquid treating agent includes but not limited to have following feature: pour point is about 30 °F to about 120 °F, it is about 50SSU to about 350SSU 100 °F of lower viscosity, vapo(u)rizing temperature is more than about 500 °F, distillation end point below about 1000 °F, the bottoms less than about 15% and the aromatic content less than about 60%.

In some embodiments, mineral oil is characterised by: pour point is about 35 °F to about 100 °F, viscosity under 100 °F is about 100SSU to about 310SSU, the vapo(u)rizing temperature of 10% is about 500 °F to about 700 °F, distillation end point below about 900 °F, the bottoms less than about 15% and the aromatic content less than about 50%.

Do not understand the liquid treating agent according to method disclosed herein at present yet completely and reduce pattern or the various modes of airborne dust.Although without wishing to being bound by any particular theory, it may be possible to the liquid treating agent applied provides enough adhesive surfaces, and the airborne dust of generation only adheres to the outer surface of processed solid.It may also be that the moist surface reducing friction is served as on processed surface, it makes clash into landing rather than give the vibratory impulse in proppant structure.Further possibility is that, a small amount of dust Control liquid treating agent applied serves as binding agent and the airborne dust caught in processed proppant surface serves as impact modifying agent to alleviate the impact of airborne dust and friction being likely to additionally produce from proppant surface.It may also be that when selected polymer is applied to some major part in the region, surface being exposed, described polymer serves as impact modifying agent to alleviate the impact that granule contacts with granule with metal or granule.It may also be that if processing procedure is not completely covered the region, surface of exposure, then the collision of the granule of uncoated granule and part coating still can make the generation of dust/broken granule minimize.Method described herein can be used for reducing the precise reason why of dust and is not necessarily important, and the result realized is important.

Method described herein can be additionally used in and applies other coating to proppant.Other coating such can be the proppant extra functional performance of offer while dust Control processes or as independent processs step.Other coating such can include following.The method may be additionally used for providing the coating not realizing dust controlling.

Hydrophobic coating.Waterproof layer has for preventing proppant reaction under down-hole acidity or alkali condition or dissolving.The chemical reaction of known support agent can cause the reduction of resistance to crushing, and by diagenetic potential fouling, i.e. the dissolving of proppant, and with the precipitating again of mineral dissolved in formation water.

Waterproof coating can be formed to form hydrophobic surface by making proppant solid contact with the alkoxy silane of one or more organic functionals.The example of the alkoxy silane of organic functional includes but not limited to aqueous or anhydrous alkyl or aryl silane.If relatively low reaction temperature and higher response speed are necessary, then it is used as triethoxysilane [(CH₃CH₂O)₃SiR] or trimethoxy silane [(CH₃O)₃SiR] and chlorosilane, wherein R represents replace or non-substituted alkyl or replace or non-substituted aryl moiety.It should be noted that, HCl can generate as the side-product of processing procedure, it may result in etching problem.Therefore, in some embodiments, anti-corrosion treatment head and handling facilities can use immediately after chlorosilane processes.

In some embodiments, if needing hydrophobic and oleophobic surface, then with fluoro alkyl-silane, proppant is processed.

If the polymer coating needing thicker crosslinking strengthens durability and hydrophobicity, can at the after-applied polymer of silane treatment.In such process, silane may include but be not limited to triethoxysilane [(CH₃CH₂O)₃SiR] or trimethoxy silane [(CH₃O)₃SiR], wherein R can include can after the surface being applied to proppant with the functional group of crosslinkable polymer reaction, or can the functional group that adheres to of Van der Waals force for polymer compatible with polymer chemistry.In some embodiments, the R group of silane includes but not limited to:

Amine (the preparation for polyurethane, polyureas, polyamide, polyimides or epoxy resin.Amine can be additionally used in polysulfones)；

Isocyanates (for polyurethane, polyurea coating)；

Vinyl (is used for and polybutadiene, styrene-butadiene, other add-on type polymerization of olefins, or reacts with by the residual vinyl in any copolymer blend of making coatings)；

Epoxide (for reacting with epoxy resin)；

Methacrylate or urea groups (for polyacrylate)；And

Phenyl (is used for and the such as PAEK containing aromatic radical polymer (PAEK) and their composite such as PEKK (PEKK)/50:50 terephthalic acids: isophathalic acid (isothallic)/unbodied polyetherketoneetherketoneketone (PEKEKK), polyether sulfone (PES), Polyphenylene Sulfone (PPSU), Polyetherimide (PEI) or poly-to phenoxide (PPO).

The polymer coating of thicker crosslinking can be prepared by: the first step is to apply silane, and second step is to dodge to be coated with polymer, prepolymer or monomer afterwards.As used in this article, phrase " dodge and be coated with " refers to the process applying reagent according to process described herein.In some embodiments, catalyst can be used for dodge the typical operating temperature of painting process and room temperature to 85 DEG C at bring out reaction.In some embodiments, methoxy silane is tended to react quickly than Ethoxysilane, and therefore methoxy silane can be used for quick flash coating.If the response speed of silane treatment is the limiting factor of suitably coating, then chlorosilane can be used as the substitute of methoxy or ethoxy silane.In some embodiments, anticorrosive can use in applying process.

In some embodiments, the method for forming the flash coating of high temperature aromatic polymer uses the slurry based on solvent or consoluet solution.Suitable solvent includes but not limited to N-Methyl pyrrolidone (NMP), dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).If remaining unnecessary solvent after the application, then they can be removed by drying steps before being sent to the container for shipping.

Scale inhibition.Multiple polymers material can be used on to suppress fouling on proppant, including the copolymer of phosphino--polycarboxylate, polyacrylate, polyvinyl sulfonic acid and sulfonated polyacrylates, or its combination in any.In the past, these polymer have to inject in stratum, and they will disperse to work subsequently in the earth formation.Referring to U.S. Patent No. 5,092,404.Such injection often leads to the inhibitor of the generation of the early stage large volume in the production cycle and returns from well.By they are applied directly to proppant as described herein, the proppant of coating can be provided with targetedly in fracturing stratum on relatively large proppant surface region, orientable scale control treatments.It is processed along with most active surface area, the effective surface area of fouling can reduce fouling in the space (i.e. hole) simultaneously preventing between proppant particles, at this space place, the negative effect that heavy dirt can be big to the flow conductivity generation of proppant.

Suitable antisludging agent includes but not limited to carboxylate and acrylate.These inhibitor can be applied to the surface of proppant in the way of similar with other functional coating of those described above.nullAnd，Suitable also has fumaric acid (CAS110-17-8)、Diethylene glycol (CAS111-46-6)、Phosphorous acid (CAS13598-36-2)、2,2 '-({ 2-[(carboxymethyl) amino] ethyl } imino group) oxalic acid trisodium salts (CAS19019-43-3)、Glycine sodium (CAS2836-32-0)、Glycine (CAS38011-25-5)、Nitrilotriacetic acid(NTA) trisodium (CAS5064-31-3)、1,2-propylene glycol (CAS57-55-6)、2-Methoxyacetic acid (CAS625-45-6)、Methylphosphonic acid (CAS6419-19-8)、Polyphosphoric acid (CAS68131-71-5)、Alkylbenzene (CAS68648-87-3)、Phosphinocarboxylic acid (CAS71050-62-9)、Trisodium orthophosphate (CAS7601-54-9)、With sodium polyacrylate (CAS9003-04-7) or its combination in any.

If owing to scale inhibition polymer is too high and need to be attached to extraly proppant surface at the dissolubility produced in fluid, then amine or ureido silane can be used as the constraint agent (tetheringagents) of acrylate and carboxylate.Chemical bond is also by adding vinyl silanes and also retaining some ethylene functionality in carboxylate, acrylate and polyvinyl phosphoric acid or polyvinylsulfonic acid and realize completely.By passing through addition peroxide in subsequent treatment and being applied to the base material of heating, peroxide can be used for the coupling causing vinyl silanes to process with polyvinyl.In some embodiments, additive can mix with inert polymer to be sprayed with give coating subtract dirt function.They also can embed in water-soluble polymer to realize time delay release scale inhibition additive.Additive can regulate by changing the swelling ratio of polymer by the crosslink density of the hydrophilic segment regulated main polymer chain or gather density from the release time of polymer coating.

Reduce friction.At present, when industry personnel mention " reducing friction ", they are talking about when fracturing fluid moves downward along well, the friction pressure produced when arriving processed stratum usually by tubular pipeline.In the mechanism reducing friction, the turbulent flow that the most received theory is considered to relate to causing because often there is, along duct wall, the oligomer or heavy polymer that stretch reduces, and the oligomer of described stretching or heavy polymer extend to the formation of the turbulent eddy that fluid is interior and destruction is in the fluid of flowing.

Proppant for reducing friction processes the form of the heavy polymer that can adopt release, the heavy polymer of described release can aid in ground dust controlling, but it is discharged into fracturing fluid from proppant, in fracturing fluid, it serves the second function reducing agent as turbulent flow.Therefore, people can create and have dust controlling and reduce the proppant of frictional behaviour.In some embodiments, can give solid these performances with same inorganic agent.

In some embodiments, use the surface that the directly coating proppant of one or more releasable or soluble polymer can pass through on proppant to deliver turbulent flow to well and reduce agent.This coating is designed to immediately or discharges described turbulent flow after one period of time delay reduce agent.If postponed, such coating can help to reduce turbulent flow in fracturing fluid and reduce the volume of polymer and avoid can with the loss of such excessive relevant precipitation and flow conductivity.Once be placed in crack by proppant, polymerization turbulent flow on original position generation proppant reduces the delayed dissolved of coating or release to strengthen control and to reduce the unexpected precipitation of polymeric reagent and the probability gathered.

Turbulent flow reduces coating and can be designed as by using water-soluble polymer for discharging immediately or discharging for time delay by adjusting the swelling water-soluble polymer of delay by those skilled in the art.nullCan be used for the material of friction reduction coating and include capryl alcohol capryl alcohol (CAS111-87-5)、Polyacrylamide (CAS25085-02-3)、The copolymer (CAS25987-30-8) of acrylamide and sodium acrylate、Acrylamide/ammonium acrylate copolymer (CAS26100-47-0)、The oleamide (CAS26635-93-8) of ethoxylation、Acrylamide/acryloyl dimethyl tauric acid sodium copolymer (CAS38193-60-1)、The polymer (CAS62649-23-4) of 2-acrylamide and 2-acrylic acid and 2-sodium acrylate、Ethoxylation-C6-C12-alcohol (CAS68002-97-1)、Ethoxylation-C12-14-alcohol (CAS68439-50-9)、Ethoxylation-C12-16-alcohol (CAS68551-12-2)、Ammonium sulfate (CAS7783-20-2)、Acrylamide (CAS79-06-1)、Politef (Teflon) (CAS9002-84-0)、Polyacrylamide (CAS9003-05-8)、Polyacrylamide-co-acrylic acid (CAS9003-06-9)，Or its combination in any.

In water not having fracturing fluid system and only having so-called " riverfrac treatment " of anti-friction agent, the concentration of anti-friction agent non-normally low (< 5 pounds/1000 gallons).In this case, turbulent flow reduces polymer and is likely to result in heavy damage, but may hinder flowing along the mantle friction in proppant pack hole and therefore reduce flow conductivity.Such situation can obtain benefit from the coating of such the second type, this coating there is hydrophobicity and/or oleophobic property so that flowing fluid self-supporting agent surface landing and pass through hole.The coating of hydrophobicity and/or oleophobic property all can allow material movement to reduce friction simultaneously.

In water not having fracturing fluid system and only having so-called " riverfrac treatment " of anti-friction agent, the concentration of anti-friction agent non-normally low (< 5 pounds/1000 gallons).In this case, turbulent flow reduces polymer and is likely to result in heavy damage, but may hinder flowing along the mantle friction in proppant pack hole and therefore reduce flow conductivity.Such situation can obtain benefit from the coating of such the second type, this coating there is hydrophobicity and/or oleophobic property so that flowing fluid self-supporting agent surface landing and through hole.Neither the coating of hydrophobicity also non-oleophobic property can allow material movement to reduce friction simultaneously.

Process by this way can also result in the trap improvement on proppant particles surface and the removal of the hydrostatic in intergranular gap.This can help to make water lock minimize, and the whole hydrocarbon therefore being improved artesian well by the amount of the power needed for reducing surface tension and removing water from hole is produced and makes hydrocarbon flow through proppant pack thing.

Super-hydrophobic coating is included but not limited to, as U.S. Patent No. 8,431,220 (being dispersed in the hydrophobicity core shell Nano filling in the polymeric matrix of elastomer) for dodging, with such hydrophobicity and/or oleophobic property reagent, the suitable material being coated with proppant；No. 8,338,351 (hydrophobic nanoparticles containing adhesion promoter group and the silsesquioxane of low-surface-energy group)；No. 8,258,206 (forging silicon oxide and/or the hydrophobic nanoparticles of titanium dioxide) in solvent；Those and the U.S. Patent No. 8,513,342 (acrylic polymerization resins, polysiloxane oil and hydrophobic particle) existed with No. 3,931,428 (the hydrophobicity fumed silica particles in resin)；No. 7,999,013 (there is fluorochemical monomer and the polyurethane resin of at least one end trifluoromethyl)；And the durability hydrophobic coating of the 7th, 334, No. 783 (solid silsesquioxane silicones), or its combination in any.Available other material include but not limited to the water contact angle aliphatic more than about 90 ° or aromatic polymer such as the polymer containing polybutadiene, there is the polyurethane of a high proportion of soft chain segment (such as fat segment), polymethyl methacrylate and silicone resin, including dimethione, or its combination in any.

Proppant use hydrophobic coating also can have the effect preventing water from arriving sand particle surface.Early it have been proved that, the flow conductivity of uncoated sand reduces with the rising of test temperature.This means that the combination that the temperature raised contacts with water is likely to destroy the integrity of sand granule and respective support agent charges.Therefore, hydrophobic coating can be used for slowing down or minimizing the detrimental effect of the temperature along with the rising observed in rich water environment as in those of down-hole existence.

In some embodiments, proppant is coated with multiple coating.In some embodiments, proppant is coated with the ground floor of hydrophobicity/oleophobic property coating, and turbulent flow afterwards reduces coating.Such multiple structure can make the proppant being processed because the separation of top layer is to reduce turbulent flow and to be reduced the skin resistance caused by the fluid flowed afterwards by lower floor.

Friction reduces coating also can adopt the form with the material rubbed between low external particle, and it serves as slip aids.Suitable material as such slip aids is with trade name POLYOX product sold by DowChemical.This material is the non-ionic water-soluble polyethylene oxide polymer with high molecular.

Tracer coating.Tracer is radiosiotope or the on-radiation chemical substance of the ad-hoc location injection in well, it is therefore an objective to they will occur with detectable level in effluent, in some position.Therefore, they achieve the fluid being injected into from the source introduced to the flowing spike flowing out logistics.Additionally, location specific tracer can be used for the given zone in artesian well/region follows the trail of the production of fluid.Generally, tracer is introduced in fracturing fluid as additive during the completion practice of the specific region being concerned.

As the conventional radiosiotope chemical substance of tracer include tritium for water (³H₂O), tritium acute pyogenic infection of nails alkane (³CH₄)、³⁶Cl-¹³¹I-、³⁵SO₄ ^2-、S¹⁴CN^-、H¹⁴CO^3-With²²Na⁺。

Conventional on-radiation tracer chemical includes halogenated hydrocarbons, halocarbon, SF₆And cobalt hexacyanide, wherein, cobalt exists with complex anion complex, because cobalt cation can be reacted in down-hole and precipitate.Various useful organic compound include sulfonic acid and the salt of these acid, smelly Camphora glycol (mapthalenediol), aniline, the aniline of replacement and pyridine.

Tracer can embed in proppant, but generally require proppant particles actual motion and leave well (i.e. the row of returning).The proppant particles of spike self be collected consequently as sample and analyze tracer in the presence/absence of.Referring to U.S. Patent No. 7,921,910 and No. 8,354,279.Other people has attempted to add in proppant resinous coat on-radiation tracer chemical, but such introducing method has needed plan the customization proppant preparation that well be manufactured before use in certain well.This can cause a problem in that because the proppant of reactive phenolic resin coating service life sometimes can be short, because tracer must discharge before phenolic resin is fully cured.

One common feature of spike proppant technology up to now is that they all need a large amount of predetermined multiple different spike proppants with production for different well area before injection.Such as, if needing five different regions of plan, then it is likely to need spike proppant five kinds different.This means that five kinds of different types of proppants must in the preparation of resin-coated factory and store in stock by proppant manufacturer or by completion practice team.

This method and process occur so fast and use the so a small amount of polymer of applying, resin or organic compound, such that it is able to use and the identical tracer applied in resin-coated equipment before, metal, salt and organic compound.Additionally, the original new polymer comprising particular functional group or oligomer before can using, such as fluorescent dye or phosphorescent pigment, even it a small amount of also can detect in the effluent produced, no matter it is water or hydrocarbon.Suitable fluorescence include coumarin, naphthalimide, rhodamine, benzanthrone, benzodiphenylene oxide ketone (benzoxanthone) and benzothioxanthene ketone (benzothioxanthrones).Phosphorescent pigment includes zinc sulfide and strontium aluminate.The coating used in the method be adjustable into so that tracer salt optionally or time delay discharge leaching from coating to subsurface environment.This is used to analyze rather than to analyze the proppant reclaimed in the row of returning by realizing effluent.Additionally, by making can to obtain in this way very short time in advance, specify the quantity of different spike sections required in certain well for greater flexibility realizing user.In some embodiments, the coating applied by process disclosed herein is moved applied immediately before the container for transporting to well site at the sand of self terminal in future.Container for tracer, it means that stock reduces.

Some the metal reagents such as stannum and copper that are used as Biocide may also function as the function of the tracer in proppant coating before.

Suitable polymer for preparing tracer coating includes the acrylic copolymer with hydrolyzable silyl acrylate functional group, as in those described in U.S. Patent No. 6,767,978.Easily describe, such polymer is by making selected from following monomeric unit at least three kinds different: the acrylate monomer of fluoride is (such as, methacrylic acid 2,2,2-trifluoro ethyl esters (matrife)), three Organosilyl acrylic monomerss (such as methacrylic acid TMS ester) and the acrylic monomers (such as methyl methacrylate) without organosilyl moiety.Three-component polymer (i.e. ter-polymers) can comprise the cross-linking agent of 0-5% weight alternatively.Such polymer is the copolymer of the product comprising following monomer:

A) monomer of following formula:

Wherein:

R is CH₃Or H, and

RF is (C)_u(CH)_v(CH₂)_w(CF)_x(CF₂)_y(CF₃)_z, wherein, u is 0-1, v be 0-1, w be 0-20, x be 0-1, y be 0-20, z is 1-3, and w and y sum is 0-20,

B) monomer of following formula:

Wherein: R is CH₃Or H, and R¹It is alkyl or aryl, and

C) monomer of following formula:

Wherein:

R is CH₃Or H, and

R¹、R²And R³Can be identical or different and be the alkyl of non-hydrolytic containing 1-20 carbon atom and/or the aryl of non-hydrolytic containing 6-20 carbon atom.

Additionally, according to chemical substance used, the tracer part containing metal also serves as Biocide, is similar to marine antifouling coating.Such as, stannum and copper are everlasting during boats and ships paint and are used as Biocide.These metals or their salt can also be added into for dodging in the acrylic acid ester emulsion being coated onto on proppant or joining the type of permanent attachment insoluble polymer to the outside of proppant surface.

Suitable water solublity and soluble polymer have description in U.S. Patent No. 7,678,872.Such polymer can dodge coating method according to this and be applied to proppant, so that swelling at polymer or the time delay release function of tracer is introduced in the fluid produced when dissolving, it is additionally operable to control the airborne dust of proppant simultaneously.

Impact modifying agent.Fine powder in well can have a strong impact on the flow conductivity of proppant pack thing.The fine powder producing 5% can reduce the flow conductivity up to 60%.Initial fine powder being distributed as before the granularmetric analysis of 20/40 sand of the pneumatic conveying of 0.03% is shown in and is transported to well site, after a handling steps, fine powder increases to 0.6%, and increases to 0.9% after two handling steps.Transport in well site may produce the significantly more fine powder relevant to impact with further handling.

Method described herein can be used for being specifically designed as the polymer-coated proppant being easier to deformation, and this will be largely responsible for reducing the generation of the fine powder of Shock-induced.These polymer decrease the quantity that granule lost efficacy when applying closure stress, effectively increase the K value of proppant, and can by keeping the packed migration reducing fine powder of spent granules.

There is the thin deformable coating at least three kinds of proppants and improve the mode of fracture condudtiviy.The first is this cargo handling process of useful process.The additive of the generation controlling/stop dust (by loading and unloading and pneumatic conveying) helps fine grain generation and mixing to minimize, and described fine grained is formed by the motion such as the abrasives as uncoated sand.Without wishing to being bound by theory, cause that the process that fine powder produces forms weak spot in each position that granule is worn simultaneously.Flow conductivity test shows have measurable ratio without the low flow conductivity of the same sand of so handling through the uncoated sand sample product of pneumatic movement.Impact resistant modified polymers coating can reduce granule and lost efficacy by extending point-to-point stress further, a generation when granule pushes another granule in the process of crack closure and the increase producing the closure stress occurred with well subsequently of described point-to-point stress.Deformable coating increase effectively the contact area between two granules.The increase of this contact area reduces the point loading attempting to make granule lose efficacy.The generation of the fine powder occurred in cargo handling process or occurred by the pressure applied in crack minimizes and will imply that there is less fine powder, and described fine powder can promote to form flow conductivity infringement.Form the equally distributed film around sand granule if dodging to be coated with, then this coating can be the effective means that prevention fine powder moves through the encapsulating of the granule of any inefficacy.Stop or minimize the motion of fine powder and can realize the control having been demonstrated to reduce the condition of the fracture condudtiviy up to 75%.

In some embodiments, for impact modified layer, this layer includes the polyurethane of relatively low Tg or lightly crosslinked polyurethane.Can pass through to use very soft polyhydric alcohol (such as having very lightly crosslinked polybutadiene based polyols) to regulate polyurethane formulations to obtain relatively low Tg and elastic preferably.Another embodiment adopts the shallow layer applying polybutadiene polymers as shock ply.Such flash coating is with based on latex or based on the preparation of solvent and for making the peroxide of the slight cured/cross-linked of polybutadiene coating apply.Other embodiment includes but not limited to include the polymer of other rubber like of polyisoprene, polychloroprene, polyisobutylene, the polyethylene of crosslinking, styrene-butadiene, nitrile rubber, silicone, lactoprene or fluorubber.Rubber or natural gum should be in water-base emulsion or dispersion or dissolve in a solvent for spraying applying.

Also by the polybutadiene coating crosslinking using catalyst or firming agent to make to have unreacted vinyl or olefin group.When catalyst, quick curing agent or have the firming agent of accelerator be introduced in method described herein process time, result will be stone tough and tensile coating.Alternatively, material can be added in be introduced into behind down-hole at elevated temperatures by the firming agent of thermal activation.This can have the effect that, the soft coating namely with rubber like prevents handling from damaging, but subsequently, the soft coating of rubber like can be converted into hard coat after being placed in down-hole and solidify at elevated temperatures.

Spendable firming agent is typically used for those of rubber, including sulfur system, with metallic soap activation sulfur system and peroxide.According to condition of cure and desired performance, it is also possible to use accelerator such as sulfonamides thiuram or guanidine.Being used as other curing catalysts to carry out similarly, it includes ionized catalyst, metal-oxide and platinum catalyst.

The delivery of additive." proppant from suspending " can have external coating, and this external coating comprises the polymer of water-swellable, and the polymer of this water-swellable changes the density of proppant with water when contacting.For example, see U.S.2013/0233545.Such coating is instructed to have the hydrogel of the about 0.1-10wt% based on proppant weight and one or more chemical addition agent can be comprised, such as antisludging agent, Biocide, gel breaker, paraffin controlling agent, asphalitine controlling agent and tracer.

In some embodiments, the method that the polymer of water-swellable can pass through to describe herein applies and exists with much lower concentration, for instance with less than about 0.1wt% or about 0.001 to about 0.07wt%.Under so low level, the coating of swellable there is no fear of generating from suspended prop, but the mobility relevant to entering crack that not processed sand strengthens can be given, also provide for dust Control simultaneously and provide delivery system when contacting with water for Biocide and tracer.Such as, the polymer coating of swellable can serve as dust Control thing when first time applies, can be swelling to strengthen position mobility, and also tracer, Biocide can be comprised or can pass through from swollen polymer, diffuse out other active component d/d after a period of time.

nullCan be used as the solubility of delivery coating and half soluble polymer includes but not limited to 2,4,6-tribromo phenyl acrylate、Cellulose-based polymer、Chitosan-based Polymer、Polysaccharide polymer、Guar gum、Poly-(methacrylic acid 1-glyceride)、Poly-(methacrylic acid 2-dimethylaminoethyl ester)、Poly-(2-ethyl-2-azoles quinoline)、Poly-(2-ethyl-2-azoles quinoline)、Poly-(HEMA/methacrylic acid)、Poly-(methacrylic acid 2-hydroxypropyl ester)、Poly-(2-methylacryoyloxyethyl trimethylammonium bromide)、Poly-(2-vinyl-1-methyl bromide pyridine)、Poly-(2-vinylpyridine-N-oxide)、Polyvinylpyridine、Polyacrylamide、Polyacrylic acid and their salt (crosslinking and partial cross-linked)、Poly-(butadiene/maleic acid)、Polyethylene Glycol、Polyethylene glycol oxide、Polymethylacrylic acid、Polyvinylpyrrolidone、Polyvinyl alcohol、Polyvinyl acetate、The sulphonic acid ester of polystyrene、Polyolefinic sulphonic acid ester、Polyaniline and polymine，Or its combination in any.

Biocidal coating.Multiple non-polymer Biocide uses in fracturing fluid.Any one in these can use in solid form, or is adsorbed in solid or soluble solid carrier, to be used as additive according in the coating being applied in of the present invention, thus giving proppant coating biocidal activity.nullExemplary Biocide includes but is not limited to 2,2-bis-bromo-3-nitrilo-propionic acid amide. (CAS10222-01-2)、Magnesium nitrate (CAS10377-60-3)、Glutaraldehyde (CAS111-30-8)、The bromo-2-cyanoacetamide (CAS1113-55-9) of 2-、Capryl alcohol (CAS111-87-5)、2,2'-ethylenedioxybis(ethanol). (CAS112-27-6)、Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate (CAS119345-04-9)、2-amino-2-methyl-1-propanol (CAS124-68-5)、Edetate (CAS150-38-9)、CMIT (CAS26172-55-4)、BIT and other isothiazolone (CAS2634-33-5)、The oleamide (CAS26635-93-8) of ethoxylation、MIT (CAS2682-20-4)、Formaldehyde (CAS30846-35-6)、Dibromo-acetonitrile (CAS3252-43-5)、Dimethyl oxazolidine (CAS51200-87-4)、The bromo-2-nitro-1 of 2-,Ammediol (CAS52-51-7)、Tetrahydrochysene-3,5-dimethyl-2H-1,3,5-thiazine (CAS533-73-2)、3,5-dimethyl tetrahydro-1,3,5-thiadiazine-2-thioketone (CAS533-74-4)、Tetra methylol sulphuric acid (CAS55566-30-8)、Formamine (CAS56652-26-7)、Quaternary ammonium chloride (CAS61789-71-1)、C₆-C₁₂Ethoxylated alcohol (CAS68002-97-1), benzalkonium chloride (CAS68424-85-1), C₁₂-C₁₄Ethoxylated alcohol (CAS68439-50-9), C₁₂-C₁₆Ethoxylated alcohol (CAS68551-12-2)；Oxydiethylene double; two (alkyl dimethyl ammonium chloride) (CAS68607-28-3), DDAC (CAS7173-51-5), 3,4,4-trimethyl oxazolidine (CAS75673-43-7), cetyl ethyl morpholine ethyl-sulfate salt (CAS78-21-7) and tributyl myristyl chlorination (CAS81741-28-8), or its combination in any.

Alternatively, can using the erodible external coating having time delay release or discharging stage by stage, the additive comprised can be dissolved and/or be discharged in down-hole subsoil water or hydrocarbon by it.Such coating can be based on such polymer, and namely this polymer is substantially insoluble in cold water but at downhole temperatures in solubilized water, and at downhole temperatures, this active substance tends to very short time after pickup and just functions to.Alternatively, external coating can be prepared by this way, so that it discharges insoluble in well fluids and when applying crack closing stress.

Can based on the crosslink density adjustment of coating by the time structure of the encapsulated composition (Biocide, antisludging agent etc.) of dispersal events.It is cross-linked to uncrosslinked polymer on a small quantity and can form rapidly-soluble coating.Highly cross-linked material can make the release of the soluble ingredient in coating more slowly.If the movement of the chemical substance being concerned in the film of crosslinking is too slow, then can add soluble filler in coating mix, such as salt, organic crystalline solid etc..Once the proppant of coating is introduced into down-hole, then granule solubilized is thus staying bigger hole as filter membrane.Referring to U.S. Patent No. 4,177,228.Insoluble polymer also is used as the insoluble external coating applied as described herein as thermosets (such as alkyd resin, partially cured acrylic resin, phenolic resin and epoxy resin) and thermoplastic (such as polysulfones, polyethers and most polyurethane).Alkyd resin as polyester may be hydrolyzed after a period of time under damp and hot conditions down-hole, and this character therefore can be utilized to realize time delay release by environment hydrolysis and environmental corrosion.The polyamide of hydrolysis and degraded also is used as such coating in time.

They and can be applied to proppant particles to prepare by being mixed with soluble filler by thermosetting polymer by coating according to various embodiments described herein.Thermoplastic film coating can so apply, and namely by dissolving in a solvent, mix with soluble filler and is coated on proppant particles by gained mixture and subsequently by employing pneumatic conveying air or be forced through the air of material of coating and be dried and remove solvent.Setting release time can by suitably selecting filler size, shape and packing density to adjust.

Biocidal polymers coating.Biocide often uses with low concentration in hydraulic fracture fluids mixture, and in fracturing fluid about 0.001%, it is corresponding to about the 0.01% of proppant gross weight.Situation and the production capacity of well are had great economic impact by microorganism.Such as, unconstrained bacterial growth can cause well " acidifying ", and in well, antibacterial produces the hydrogen sulfide refuse as they metabolic functions.Such acid gas in the fluid produced is very less desirable and can be the corrosion in production equipment and the root for the cost from the hydrocarbon desulfurization produced.

Therefore, in some embodiments, Biocidal polymers can be applied to described proppant as the auxiliary agent of dust controlling and suppression down-hole bacterial growth.Can be used as the suitable polymer of Biocide to include: acrylate copolymer, sodium salt (CAS397256-50-7) and formaldehyde, polymer (CAS63428-92-2) containing methyl oxirane, 4-nonyl phenol and oxirane, or its combination in any.

Additionally, according to the chemical substance adopted, the metal as marine antifouling coating also is used as the Biocide on proppant.The stannum being such as everlasting in marine paint to use as Biocide and copper.These identical reagent can be coupled to be coated onto on proppant as biocidal coating for sudden strain of a muscle in acrylic acid ester emulsion.

Sulfide controls.Hydrogen sulfide is toxic chemical, and it is corroding metal also.Due to the safety increased and anticorrosion demand, in hydrocarbon reservoir, the existence of hydrogen sulfide adds the cost of production, transport and refine.When drilling well as the additive in mud or as the composition in flushing process, sulfide scavanger is often used for removing sulfide.

Concentration according to hydrogen sulfide in fracture-type reservoir, the concentration of the scavenger that proppant surface comprises can change to remove hydrogen sulfide more or less.In enough volumes, concentration can be reduced to, from the level (in the scope of 500-1000ppm) causing safety hazard, the level (1-20ppm) that sulfide is only a kind of fulsome material by the proppant with sulfide Scavenging activity.If proppant's surface area is big and the good dispersion of scavenger, then high performance vulcanization H-H reaction and clearance are possible.

Time delay releasing dosage can pass through to comprise mantoquita in proppant according to the present invention, such as curpic carbonate (CuCO₃) deliver, can be very slowly delivered in crack to process hydrogen sulfide namely can reach the steel beam column in wellhole at hydrogen sulfide before.

Zinc oxide (ZnO) and ferrum oxide (Fe₂O₃) it is directly used as the solid particle processing hydrogen sulfide.These can join coating proppant surface on or be formed as the functional stuffing in the proppant coating that applies.The use of high surface area fillers or even nanosized particles can be used for making the area of the interaction between hydrogen sulfide and metal-oxide to maximize.

Oxidant is also useful, such as the oxidant of solid form.Exemplary materials includes solid permanganate, quinone, benzoquinone, naphthoquinone, and comprises the reagent of quinone functional group, such as chloranil, 2,3-bis-chloro-5,6-dicyano benzoquinones, anthraquinone etc., or its combination in any.

The polymer with side aldehyde radical can also be used for introducing in proppant coating aldehyde degree of functionality being used for controlling hydrogen sulfide.Polyurethane can be made with such degree of functionality.Referring to U.S. Patent No. 3,392,148.Similarly, may be formed to have other polymer of side aldehyde radical, such as polyethers, polyester, Merlon, polybutadiene, hydrogenation polybutadiene, epoxy resin and phenolic resin, or its combination in any.

Additionally, dendrimers can be prepared to has the multiple terminal aldehyde groups that can be used for reaction.The dendrimers of these rich aldehyde can be used as filler, copolymer or alloy and the coating as coating or layering applies to proppant.

Dioxole monomer and polymer allow this degree of functionality to introduce as the pendant groups in polymer.Such dioxane functional group may act as oxidant to control the generation of hydrogen sulfide.The homopolymer of dioxole and the copolymer of dioxole and Fluorine containing olefine, acrylate, methacrylate, acrylic acid etc. can be used.

Amine and triazine also serve as the scavenger of hydrogen sulfide.Can use polymer or dendrimers that amine terminates and its have and be crimped to polymer, the advantage that therefore they can be held in place in proppant coating.Namely high functionality by using dendrimers to realize, can use every multiple functional group of single polymer molecule.

Triazine can be added in urethane crosslinks bridge by isocyanates is connected to the R group of triazine.Referring to U.S. Patent No. 5,138,055 " s-triazine crosslinking agent of urethane official energy ".By changing the ratio of OH group and using three alcohol functionalities and simple function triazine isocyanates also can prepare side triazine.These functionalized polymer can add as filler or self controls to realize dust controlling and down-hole hydrogen sulfide as coating preparation.

That some in metal carboxylate and chelate are based on zinc or ferrum or comprise zinc or ferrum, they can be applicable on proppant to remove hydrogen sulfide.Referring to U.S. Patent No. 4,252,655 (organic zinc complex in drilling fluid).These carboxylates or chelate provide with water soluble complex form in proppant coating, and described water soluble complex and hydrogen sulfide will form insoluble petal sulphates when situ downhole interacts.

Hydrogen sulfide also can by the polymer controls with the functional group that may act as ligand.With other polymer, as mixed in described elsewhere herein those, and can apply to proppant particles as coating with the polycarboxylate forming carboxylate metal ester complex by metal pretreatment.This other polymer being also applied for there is the functional pendant groups such as amine and the ether that serve as sulfide complex ligand.

In some embodiments, the metal controlled for sulfide is not intended as complex and is present in main polymer chain so that the removal of metal not necessarily can relate to the decomposition of polymer.The polymer with metal side chain complex can be used.Two such examples of this material are polyethylene ferrocene, poly-ferrocene acrylate.In some embodiments, it is possible to use the main chain polymer containing metal, but this polymer can be degraded when reacting with hydrogen sulfide.

If wrapping hydrogen sulfide containing production fluid under alkaline ph values (namely pH value is more than 7 or more than 8-9), most of hydrogen sulfide will exist as HS-anion.In this case, anion exchange resin or molecular sieve can be used for from described fluid extraction HS-anion.Molecular sieve or anion exchange resin can use as active filler in the propping agent combination of resin coating, and it includes aluminium silicate such as clinoptilolite, modified clinoptilolite, Vermiculitum, montmorillonite, bentonite, chabasie, heulandite, foresite, sodalite, analcime, phillipsite, permatite, brucite, A type molecular sieve, X-type molecular sieve and Y type molecular sieve；Silicic acid antimony, silicotitanate；And sodium titanate, and at US8, those listing in 763,700, the disclosure of which is incorporated herein by reference.As at US8, described in 763,700, suitable ion exchange resin is typically divided into storng-acid cation exchange resin, weak-acid cation-exchange resin, strong-base anion-exchange resin and weak-base anion-exchange resin.The hydrogen sulfide produced by biologic activity by use (as above) Biocide and biocidal coating and removes sulfate anion (HSO₄ ^-Or SO₄ ^-2) control.Anion exchange resin can be used for removing sulfate.Nitrate can also be used for destroying the antibacterial conversion to sulfate.Nitrate also can add in the coating and prevent nitrate from discharging too early by that easily lose or semipermeability coating afterwards, thus realizing the slow release of nitrate.

Composite coating.In some embodiments, described method effectively carries out serially, and such method provides a kind of and has cost-benefit method to apply the laminated coating with different compositions and different functional attributes.Various combinations are all possible.Such as, in some embodiments, can using multiple shower nozzle, each shower nozzle can apply different preparations.If coating agent in succession is chemically incompatible, because the nonwetting layer being coated with below of the layer applied, then can use one or more silane coupling agents, for instance have the surface similar to the inconsistent layer of said two can and or the block of solubility parameter or graft copolymer to obtain better interface cohesion.If it is desire to be multiple layers, then different shower nozzles may be additionally used for applying identical preparation.Some examples of composite coating include following.

For improving two layers of proppant physical property.Apply to have the different pantostrat of different performance characteristics, such as hard urethane layer (urethane, cross-linking agent (such as poly-ethylene imine) and isocyanates), be followed by softer outer urethane layer.This coating structure can realize some compressions and combine for proppant particles because of soft outer layer, but limits further compression/crushing due to hard internal layer.Relatively soft outer layer also can tend to reducing impact damage and the abrasion on the relative handling loading and unloading proppant and conveying equipment after applying sudden strain of a muscle and being coated with between granule.

Continuous multilayer for time delay release function.Continuous multilayer can be used for adding the ground floor of the additive with the first function, adds afterwards to have and controls environmental liquids when and how close to the second layer of the performance of ground floor additive material.Such as, the soft lightly crosslinked urethane layer with Biocide additive is coated with the hard urethane layer comprising soluble granule.When soluble granule is removed, outer layer forms semi-permeable coating, and it allows the following slow diffusion killing bio-additive.

It it is the multilamellar of the polymer of weak binding after the strong polymer combined.Silane treatment for silicon dioxide compatibilized can apply the outer surface to sand proppant.It is with containing functional additive such as Fe after this process₂O₃The interpolymer layer coating of microgranule, to realize the removing of sulfide.Outer coating comprises the loose combination polyacrylamide to the first coating.One arrives down-hole, and polyacrylamide is just released and on the inner surface of the metal tube that is gathered in well.This preparation can realize the control that friction reduces and provides sulfide level in the whole life-span of well in a short time, until ferric oxide particles is completely depleted.

Discharge coating stage by stage.Such as, when the life cycle of well starts, the corrosion relevant to oxygen and asphalitine are usually easier to go wrong, and growing of antibacterial can occur subsequently in the life cycle of this well.The composite coating of three layers can solve the development of this delay.Ground floor, innermost coating such as can comprise kills biological function.Second layer coating can comprise such as asphaltene inhibitor, and third layer can comprise the polyol of such as loose combination as oxygen scavenger.Low oxygen level can drop in the outer layer of this proppant at once, and particularly in the region of dead band/limit from the porch of well flowing, these areas can not by the fluid flushing containing oxygen scavenger.When well starts to produce time, outer layer can be consumed from surface and corrode, thus exposing the asphalitine inhibition layer of sulfonated alkyl phenol polymer, asphalitine inhibition layer is etched as well as the time or dissolves.Along with well continues to produce, asphalitine problem can reduce, the coating of remaining inner side can its Biocide of slow release to guarantee the lasting kilter of this well.Single composite provides the benefit of these extensions, namely introduces as mixture that in well, to have difference in functionality multiple proppant is lower in cost and logistics is easier to than using.

Time delay release coating.The external coating being made up of the polymer of sol particle and/or solubility or erosibility is used to can be used for providing the controlled time delay release of functional additive, like the enteric coating being medicine.Different from discharging structure stage by stage, time delay release coating does not have the release of second stage.It is essential that the proppant according to the coating of the present invention provides in time, in original place and the release in whole fractured subterranean formation.Exemplary functions additive can include Biocide, antisludging agent, tracer and sulfide controlling agent.Suitable water solublity or soluble polymer has description in U.S. Patent No. 7,678,872.Erodible host material comprises one or more cellulose derivatives, water soluble or be insoluble in crystal or the amorphous form of water.

The time structure that the component of encapsulation is discharged by diffusion can adjust as desired by the crosslink density adjusting encapsulation coating and revise.There is the polymer being seldom linked to without cross-linking and present before release rapidly-soluble coating at short notice.Highly cross-linked material can have the soluble component rate of release in much lower coating.If the movement that the chemical substance being concerned is in cross linking membrane is too slow, then soluble filler such as salt, organic crystal solid etc. can be added into coating mix.Once the proppant of coating is introduced in well, granule can be dissolved, and leaves bigger hole, the same with the phenomenon that the filter membrane in the U.S. Patent No. 4,177,228 of by name " production method of microporous membrane for defecator " occurs.If lightly crosslinked or hydrogel, then polymer is swelling and will realize the controlled diffusion of additive of encapsulating.

Insoluble polymer, as thermosets (such as alkyd resin, partially cured acrylic resin, phenolic resin and epoxy resin) and thermoplastic (such as polysulfones, polyethers and polyurethane) can be used as shallow layer together with soluble additive.The mixture obtained applying by being mixed with fine grained soluble solids by such as thermosetting polymer and can be prepared by such coating to proppant particles.Thermoplastic can by applying mixing in thermoplastic polymer dissolution solvent, in fine grained soluble solids and being coated with proppant with mixture.Then being removed by solvent at drying stage, this stage can be only the air-flow of crossing current.Time before release can based on size, shape and solid concentration adjustment.

In some embodiments, process described herein provides from the formation polishing coating, can should dissolve over time from polishing coating, or when fluid is etched through coating surface.The acrylate copolymer with hydrolyzable silyl acrylate functional group is included for the suitable material of such coating.(referring to U.S. Patent No. 6,767,978) can also use the alkyd resin as polyester, because they tend to be hydrolyzed over time under condition in well, and therefore gives delay releasing mechanism by the combination of hydrolysis and corrosion function.

Cellulosic coating is also provided that time delay release coating.It is suitable that and include but not limited to hydroxy alkyl cellulose class, such as hydroxyethylmethyl-cellulose and hydroxypropyl methyl cellulose (being also referred to as hypromellose).Suitable material can be purchased from DowChemical with trade name METHOCEL.The cellulose ether that this material is made up of water-soluble methyl cellulose and hydroxypropyl methyl cellulose polymers.Also by use hydroxyethyl cellulose reagent as can from DowChemical with those being purchased of trade name CELLOSIZE to realize rheology modifying.

Be used as can in well the polyamide of Water Under solution.

Acidproof/alkaline-resisting coating.In fracturing, the chemical erosion of proppant is the thing being concerned.For silica sand, the acid number of proppant is typically used to characterize the quality of this sand.The concrete test under acid exposes of test description in the 8th part of the ISO13503-2 proppant sand, as the method determining its suitability under specific well condition.If the component in sand or impurity dissolve under sour environment or instability, then proppant particles will obtain porous and present relatively low entire compression fragility.Therefore, it may be desirable to be that there is such coating, namely this coating can minimize by the acid erosion to silica sand existed in the subsoil water of down-hole.

Aqueous slkali also can dissolve or Partial digestion silica proppants and the resinous coat on such proppant, particularly under the pH value of 9 or higher.This can cause that the flow conductivity of the proppant pack thing being placed in crack goes wrong, and this is that the granule owing to causing because of the dissolving of granule outer layer weakens and possible particle diameter reduces.

Ceramic proppant as diagenesis and be subject to high-alkali or peracidity water erosion, diagenesis is that wherein pottery is dissolved in aqueous solution under stress, then with the phenomenon that again precipitates of other element that exists in fluid.The solid formed again can not be tough or be of the same size as original ceramic proppant, and the impact of the flow conductivity of ceramic proppant charges can be issues that need special attention by it.

In some embodiments, the coating applied is acidproof, alkaline-resisting or acidproof and alkaline-resisting, and protection that can be new to the offer of all types of proppants, and the type of described proppant includes but not limited to sand and ceramic proppant.Some the resistance to acid polymers that can apply include: polypropylene, acrylate copolymer, and most of fluoropolymer.Owing to the covering of the whole superficies of proppant is increased, the quantity according to equipment used and dispersing nozzle, it may be necessary to apply repeatedly to be coated with to same matrix polymer.Method described herein is repeatable, until being applied with appropriate number of coating.

Suitable alkaline-resisting polymer includes polyolefin, some fluoropolymers (except PVDF and FKM is not resistance to especially highly basic) and much polyurethane.

Corrosion inhibitor.At gas industries, in down-hole application, metal erosion is a significant problem.Can corrode by acid Induction Process or by oxidation.Acid condition can because of the acid treatment on stratum, generation acid or H₂The antibacterial of S or can be dissolved in water under stress to form the CO of carbonic acid₂Cause.Oxidation/the oxide etch of metal can occur when water and oxygen exist.

Corrosion in down-hole application solves often through interpolation corrosion inhibitor and/or acid scavenger in drilling well, completion or hydraulic fracturing process.Corrosion inhibitor provides and makes to be exposed to the coating of the passivation of metal surfaces of fluid.Micromolecular passivation layer applies also by following manner, namely by adding these molecules in treatment fluid, then passing through use Coordinative Chemistry method makes described molecule be attached to metal, for instance utilize the combination of the active coordination site on organic molecule or polymer to apply to the mode of metal.Acid scavenger is the alkali compounds accepting acid.After initial management, use the fluid routine cleaning containing such material or flushing, be also by common method controlled for corrosion maintenance.

Oxygen scavenger is used to remove, from downhole fluid, the oxygen dissolved.Once completion, oxygen is usually no longer big problem, this is because oxygen is typically not present in producing formation, but oxygen can be a problem in drilling mud and fracturing fluid.Oxygen scavenger is used in these fluids during drilling well, pressure break and completion.

Often use for metal surface to prevent the polymer coating corroded and its to be applied to metal before metal uses.Resin or the epoxy coating dried are exactly two examples, but other polymer also can use on metal.When possible; cathodic protection is used also by following manner; namely by being placed around more reactive metal at claimed metal, and more reactive metal and the chemical reaction in fluid or oxidation described in utilizing, rather than with expect protected metal reaction or oxidation.Zinc, aluminum and other be used to cathodic protection than the more reactive metal of ferrum (Fe).

nullCan apply to solid to include chlorination-1-benzyl quinolinium (CAS15619-48-4) for the chemical substance of corrosion protection、Acetaldehyde (CAS57-07-0)、Ammonium bisulfite (CAS10192-30-0)、Benzylidene acetaldehyde (CAS104-55-2)、Oleum Ricini (CAS8001-79-4)、Anhydrous cupric chloride (CAS7447-39-4)、Fatty acid ester (CAS67701-32-0)、Methanamide (CAS75-12-7)、Octoxynol 9 (CAS68412-54-4)、Potassium acetate (CAS127-08-2)、Propargyl alcohol (CAS107-19-7)、Propandiol butyl ether (CAS15821-83-7)、1-(phenyl methyl)-pyridine (CAS68909-18-2)、Ready denier oil acid (CAS61790-12-3)、Tar base、Quinoline、Quaternized Methoxybenzyl chloride (CAS72480-70-7)、With triethyl phosphate (CAS78-40-0)、Or its combination in any.

Corrosion inhibitor as solid can be mixed in resin formulation as filler, then apply to proppant with formed can in down-hole either directly through the coating of corrosion protection.Coating can be designed to provide at once corrosion protection, as during drilling well or completion to oxygen scavenger institute it may be desirable to.Coating also can be modified to time delay release corrosion, as discussed above.Cathodic protection realizes also by comprising one or more metallic particles (Zn, Al etc.) in the recovered water/halogen of high conductivity.

Corrosion inhibitor as liquid can be introduced in these systems by selective polymer proppant coating, and in described polymer support agent coating, liquid/organic chemicals is mixable or sl. sol..Some examples include the glycol amine mixed with polyacrylamide or lightly crosslinked or thermoplastic polyurethane.

Other polymer, as 2-vinyl-2-azoles quinoline is used as water-soluble polymer filler, it can be encapsulated in the resinous coat on proppant, and dissolves from coating over time.Then this shla molecule can make passivation of metal surfaces, and suppresses acid corrosion.

Acid scavenging capacity can be provided by the flash coating of the polymer with sour clearsanattribute.Such as, having nitrogen-containing hetero bond thing such as polyvinylpyridine and polyvinylpyrrolidone, carboxylate or side base amine can provide such acid scavenging capacity, and namely nitrogen can interact with acid to generate salt.The Scavenging activity of these polymer can be relevant to the concentration of functional group on polymer, and to these groups in order to produced fluid reaction remove the mobility of acid impurities and obtaining degree is relevant.

The improvement of resistance to crushing.The aqueous based dispersions of pre-cure urethane can mix with polyurethane cross-linking agent such as poly-ethylene imine, isocyanates or carbodiimide to generate the coating hard, crosslinking of low concentration.Personnel as only having ordinary skill level are known, and the character of cross-linking agent and the difference of quantity realize adjustment and the amendment of the solidification level to coating, are for hardness more or less, crosslink density, glass transition temperature and infiltration rate.In some embodiments, 0.5% or 0.1～0.3wt% of coating level up to the weight based on the proppant that can be applied in every time processed.In some embodiments, if it is desired, apply multiple coating to form thicker coating.In some embodiments, proppant has, or at least has 1,2,3,4,5,6,7,8,9 or 10 layers of coating.

Relative to undressed proppant sand, even the proppant sand processed through polyurethane also obtain the resistance to crushing (" K value ") of enhancing under low coating level.Referring to table 3 below.Other type of thermoplasticity also should present similar result with thermosetting polymer coating.

Table 3

Carry out the K value of self compaction test, according to ISO13503-2

PU coating weight	Extruding test, K value	Improvement compared with roughing sand
			0% (untreated 20/40 sand)	6	0% (comparison)
0.25%	7	17%
			0.25%	7	17%
0.31%	7	17%
			0.50%	10	67%
0.53%	10	67%

Paraffin inhibitor.Paraffin is long-chain hydrocarbon, is generally C18 to C100 or bigger (18 to 100 carbon), its change that usually can occur because of the temperature or composition that reduce paraffin dissolubility in hydrocarbon fluid, thus from hydrocarbon solution precipitation out.Once precipitation, these paraffin may form wax with crystallization and pile up.

In some embodiments, paraffin inhibitor can be applied within proppant or on.Such coating just implements process before having begun to precipitation or crystallization at paraffin in fractured subterranean formation and at the temperature of the rising of down-hole existence.By inhibitor being introduced in fractured subterranean formation when paraffin is still solvable, the hydrocarbon stream produced when it moves to surface and merges with other pressure break logistics for reclaiming when the hydrocarbon stream generated cools down and/or mixes with water, and now this process can affect the crystalline rate of paraffin.Such condition frequently results in paraffin dissolubility and reduces and form paraffin precipitation and crystallization becomes the condition of problem.

The paraffin inhibitor of the present invention can add by the additive as the polymer coating on proppant or as release.The polymer of coating can keep being connected with proppant particles, until proppant is exposed to hydrocarbon, when being exposed to hydrocarbon, polymer can be dissolved in the hydrocarbon/water effluent of hydrocarbon or mixing.Be included in type discussed above time delay release or stage by stage the releasable additive in release coating paraffin suppressant additive is discharged in time, this is by diffusing out from coating that is swelling or that dissolve or the coating of the opening for evacuating paraffin wax additives by having stayed from the sol particle of coating migrates out and realizes.

Can be used as the polymer of paraffin inhibitor to include, for instance styrene esters copolymer and trimer, ester, phenolic resin, many alkyl phenols and Fumaric acid-vinyl acetate copolymer.The length of the molecular weight and side chain that regulate inhibitor can be used for changing inhibiting character.These characteristics affect crystalline rate and the distribution of sizes of paraffin crystal, and therefore affect the pour point of gained solution.

Can by adding solvent to increase the dissolubility of paraffin and therefore to reduce the crystalline rate of paraffin crystal and total crystallization distribution of sizes reduces the pour point of paraffin to hydrocarbon mixture.These are usually the copolymer of acrylate and allyl ether, urea and derivant thereof, have the ethane-acetic acid ethyenyl ester main chain of unsaturated dicarboxylic acid imide, dicarboxylic acids amide and dicarboxylic acids half amide.

The polymer that can be used for paraffin crystal modified includes vinyl-vinyl acetate copolymer, acrylate polymer/copolymer and maleic anhydride multipolymer and ester.

Paraffin dispersant causes that by changing paraffin crystal surface paraffin particles is repelled and works, and therefore suppress can the formation of bigger paraffin aggregate of suspension sedimentation from reservoir fluid.Typical chemical substance includes alkene sulfonic acid ester, poly-alkoxylation thing and ethoxylated amine.

Asphaltene inhibitor.Asphalitine is complicated polycyclc aromatic compound, and it often has heteroatom and has aliphatic side chains.They in many hydrocarbon reserves concentration from < 1 to 20% change.They dissolve in benzene or aromatic solvent, but insoluble in low-molecular-weight alkane.

Asphalitine have with paraffin class like problem because they are usually soluble in oilfield reservoir in the hot hydrocarbon mixture of pressurization, but the change of temperature and pressure can cause precipitation or flocculation in the process produced by this reservoir.Any one in both can have the effect reducing fluid flowing or have the effect making fluid stop flowing completely in the worst case.Once asphaltene precipitation, this well must flow through application pressure reduction or by cleaning with toluene, dimethylbenzene or other suitable aromatic solvent mechanically to swipe or to knock precipitate and repair.Cleaning is expensive and to stop well in this process, and therefore for the owner of well and operator, the asphalitine additive carried by the proppant processed demonstrates huge economic benefit.

Asphalitine controls by using dispersing additive or inhibitor.Dispersant reduces the particle diameter of precipitated asphalt matter and makes them keep suspending.Dispersant often after asphaltene precipitation is likely to occur, namely along with oil move into from reservoir produce passage and pressure decline or temperature decline after certain point be used as fracturing fluid additive.Dispersant is usually the surfactant of non-polymer.Some asphaltene dispersants used in fracturing fluid include: the alkylaromatic hydrocarbon of extremely low polarity；Alkyl aryl sulphonic acid；Phosphate ester and phosphine carboxylic acid；Sarcosinate；Amphoteric surfactant；Ether carboxylic acid；Aminoalkyl carboxylic acid；Alkyl phenol and their ethoxylate；Imidazoline and alkylamine imidazoline；Alkyl succinimides；Alkyl pyrrolidone；Fatty acid amide and their ethoxylate；The fatty acid ester of polyhydroxy-alcohol；Imines ion is to salt and organic acid；And ionic liquid.

Inhibitor actually stops the polymerization of asphaltene molecules and prevents precipitation.Asphaltene inhibitor is usually polymer.Commonly used in fracturing fluid common asphaltene inhibitor includes: the sulfonation variant of alkyl phenol/urea formaldehyde and these resins；There is the polyolefinic ester of alkyl, alkyl phenyl or alkyl pyridine functional group, amide or acid imide；The copolymer of thiazolinyl/vinylpyrrolidone；The graft polymers of polyolefin and maleic anhydride or vinyl imidazole；Hyperbranched polyesterimide；Lignosulfonates；And poly-alkoxylation asphalitine.

The asphaltene inhibitor of polymerization can be introduced directly into as the coating on proppant particles.They can apply as such coating, described coating can discharge immediately in a controlled manner or by time delay discussed above discharge coating and stage by stage discharge coating carry out slow releasing in time.

Asphaltene inhibitor also is used as the additive in polymer coating.

Asphaltene dispersants can be mainly used as the composition/filler in coating to be released in time.According to whether wish release or time delay releasing dosage immediately, their release in time can control by coating discussed herein.The branched polymer with the arm comprising dispersant function is used as, and wherein side chain is connected to main polymer chain with release dispersant by reactive group such as ester, the hydrolyzable group etc. that can degrade over.

The advantage directly using asphalitine controlling agent on proppant particles is that these reagent can discharge in the earth formation before asphaltene precipitation.Such original position delivers the effective process achieved before problem occurs and under controlled concentration.

Fines migration controls.Except the equipment attrition being derived from handling of higher resistance to crushing and reduction, the flash coating of the present invention can also help to control the fines migration of down-hole thus helping to maintain flow conductivity.

Can filling a part of intergranular space rate by the fine powder of the broken generation of proppant pack thing, this is directly related with flow conductivity.The more important thing is that fine powder can move under the pressure of conditions down-hole in fluid production process and cause a large amount of infringement, occasionally result in flow conductivity and reduce more than 75%.

The impact of fines migration standard flow conductivity test in and inconspicuous because this test is to carry out under the flow rate of too low mobile fine powder.Some can by being applied to proppant to the processed outside viscosifier of proppant applying to the control of down-hole fines migration, and these outside viscosifier will catch the fine powder run in down-hole.Afterwards, in fracturing process, the proppant of coating is placed in well.Which ensure that fine powder control processes and implement at the surface of the particles and ensure that the degree of depth in coating infiltration crack is equally deep with proppant particles exactly.

Can be used for the conventional tackifier resins of the control of the fine powder on proppant or resin dispersion includes: a) from the side-product (Talloil rosin) of the rosin resin (wood turpentine) of veteran stake, resin (gum rosin) or paper technology；B) from the hydrocarbon resin of petroleum-based feedstock, aliphatic (C₅), aromatic (C₉), bicyclopentadiene, or these mixture；And c) from timber resources or from the terpene resin of citrus fruit.

Anion/halogen is removed from recovered water.Halogen especially bromine can cause going wrong in recovered water because reacting generation chemical disinfection byproducts compound with disinfectant.For bromide, the concentration value of 0.1mg/L has the risk generating unexpected side-product.These side-products may also be potential carcinogen.Such as, some byproduct compounds have the toxicological profile of human carcinogen, and their four kinds are by control, for instance bromodichloromethane, dichloroacetic acid, dibromoacetic acid and bromate.

In the context of the present invention, can by among the resinous coat on proppant or on add anion exchange resin and carry out the removal of bromine.In order to adhesive type is attached in the surface having been coated with, such exchanger resin can add during application is dodged as described herein and is coated with or add when coating is dry when dodging and being coated with and terminate.

Method described herein and compositions process various proppant solid when being highly suitable for outside regular resin coating operation or equipment.So, the method can such as suppressing at least some of such as major part of proppant solid that the liquid treating agent of dust applies to bulk blend as uncured coating.Such processing method gives such probability, and namely this process can be used for providing extra performance without based on the regular coating procedure manufacturing equipment for proppant solid.The additional function of such type our application number be 10/872,532, name be called the U.S. Patent application of CO-PENDING of " difunctional proppant " present U.S. Patent No. 8,763,700 has description, the disclosure of which is incorporated herein by reference.Such additional materials can include such as providing in the coating the painted as seen pigment of amount, colorant, dyestuff and filler.Other material may include but be not limited to reaction promoter or catalyst, cross-linking agent, brightener, Allyl carbonate, coloring agent, fluorescent agent, brightening agent, UV absorbent, hindered amine as light stabilizer, defoamer, processing aid, Muscovitum, Talcum, Nano filling, impact modifying agent and lubricant.Other additive spendable may also include such as solvent, softening agent, surfactant, for removing the molecular sieve of reaction water, diluent and/or binding agent.Described additive can exist with about 15% weight or less amount.In one embodiment, the about 0.005-5% that amount is coating composition weight that described additive exists.Methods described herein can be additionally used in increase other function as described herein.

Proppant as herein described can be used in gas well or oil well.Such as, proppant can be used in the subsurface formations split to strut crack and to utilize the performance of proppant in the process producing oil and/or gas from well.In some embodiments, proppant contacts with the subsurface formations split.Can adopt and proppant and/or sand are introduced any traditional method in gas well/oil well make described proppant and contact with the subsurface formations split.In some embodiments, it is provided that proppant is introduced the method in gas well and/or oil well.In some embodiments, the method includes being placed in well proppant.

Embodiment

Embodiment 1

Existing sand factory utilize the not good spray pattern of design carry out invalid initial testing.The described multiple positions being sprayed at along conveyer belt apply.Recognize if sand is not heated, then people would be less than being likely to the inorganic agent that adds in water more than 0.5%.The coating efficiency difference tested is to can not correctly evaluate the effectiveness being test for inorganic agent.

Embodiment 2

In a second embodiment, when sand is used to the blender stirring of coated sand, manual by inorganic agent solution applying to sand, described blender is the same with the equipment used in tradition coating procedure.If this method focuses on uniformly applied, whether this technology can be effective.Be low to moderate at the mineral oil of up to 0.5% (by weight) or concentration the dilution of 0.12% (by weight) polymer solution level under test applying level.

Result shows, even if ideally applying, the concentration of 0.5% (by weight) is also likely to the particle surface forming overly wet profit and brings problem by being likely to when moving processed proppant with tradition handling facilities.The concentration of 0.25% is found to be effectively, but it is just somewhat invalid to be further reduced to 0.12%.

Embodiment 3

With containing acrylate copolymer and alcohol alcoxylates (from RohmandHaasChemicals, LLC, 100IndependencemallWest, Philadelphia, PA19106 are purchased with trade name ROHMINDC-5500 emulsion) mixture with the uncoated proppant sand not heated of the rate process of 0.25wt%.This inorganic agent is applied by the multiple nozzles being positioned on the either side of the sand curtain fallen from conveyer belt.Described nozzle forms the taper smog of thin spraying, and it clashes into the sand solid of whereabouts when the sand solid fallen falls into such accepter, and described accepter turns to the pneumatic testing tube of supply to enter open-top receptacle through a series of.Set the position of some nozzles to process the upper part of the stream leaving described band, and other spray from below with the downside of coated particle stream.

All processed sand keep touching up dry and free-flow.It is absent from the superfluous cognizable caking of inorganic agent, gathering or alluvial.

Compared with untreated normal sand, treated sand demonstrates the airborne dust level risen from uncovered discharge chamber substantially to be reduced, i.e. subjective reduction 50-80%.See that the solid rapid subsidence with ambient air flow rising produced by discharging returns in open-top receptacle.

Embodiment 4

As described in embodiment 3, identical inorganic agent is used to process uncoated fracturing sand at commercial sand handling facilities place.Process nozzle and be arranged on annular sprayer (as in figs. 5 and 6) and guide their conical jet pattern, inorganic agent is applied to the sand fallen with ratio essentially identical in embodiment 1.Treated sand is subsequently by static mixer that construct as shown in FIG. 7, type shown in Fig. 3 and 4.All of process carries out at ambient temperature.Range estimation shows that treated sand presents the essentially identical obvious reduction of the airborne dust from uncovered discharging, and the dust that ambient air flow carries up settles rapidly and will not run out of discharge region.

Embodiment 5

Proppant described in embodiment 3 and 4 is measured test and contrasts treatment effect with the sand with untreated 30/50 size.Result is shown in lower section table 4.

Table 4

Although said preparation applies so quick, described process provides the improvement in resistance to crushing and significantly reducing in turbidity.Turbidity is related to the ratio of the little solid in the solution that suspends.The display fine powder that reduces of turbidity is not dispersed in solution in treated sample, but is captured or is gathered in proppant.This display adopts additive treating to be effective for minimizing of fine powder movement in the solution and change into and aerial mobile reduce (with untreated sand facies ratio, the dust that treated sand enters in air after handling reduces).

Also finding, the coating applied also enhances the treated proppant repellence on the impact of acid (hydrochloric acid of 12% and the mixture of 3% Fluohydric acid .), and also increases the K value (resistance to crushing) of treated proppant.

Embodiment 6 and 7

Carry out the compatibility that additional testing measures some characteristic of the fracturing fluid that the dust Control to sand processes and tests.Fracturing fluid uses guar gum, and it is a kind of natural water-soluble polymer.

Embodiment 6 is the crosslinking test using the borate crosslink in 200 °F of deionized waters to compare with the borate crosslink in the water containing dust Control component.Primer is the borate crosslink of the polymer loading amount of 20/1000ths (ppt) and 2.2/1000ths grams (gpt).This system is buffered to pH and cross-links more than 8.5 and afterwards with borate solution.Dust additive is concentration is the ROHMINDC-5500 of 0.25% weight.Described sand is coated.

Described test starts from the slurry of water and the sand of 4 lbs/gal processed by the emulsion containing acrylate copolymer and ethoxylated alcohol mixture.This slurry under agitation heats one hour under 200 °F.At that time, all can be able to be moved into water from any material that this coating is extracted.It is used to prepare fracturing fluid system after separating described sand and described water from water afterwards.

PH value under the above-mentioned polymer volume specified and in comparison deionized water is when 6.67, and the viscosity of fracturing fluid is initially 15.4 centipoises (cp).When with borate crosslinked, pH value is 11.05.

Under 15.4cp, the pH value in comparison deionized water is 6.67.When with borate crosslinked, pH value is 11.05.Under 15.2cp, process pH value is initially 8.06 and is 10.70 when crosslinking.

Table 5

Viscosity data displayed in Table 5 illustrates that control sample (preparing in deionized water) has the rheology situation closely similar with the fracturing fluid prepared with the water after being exposed to chemicals used in this dust Control processing procedure.These tests demonstrate, and for deionized water and treated water, after adding cross-linking agent, viscosity all increases to > 300cP.Therefore, cross-linking reaction is equal in the deionized water or do not have with dust Control additive.This test result demonstrates chemical substance used in the process of the method will not change or hinder the rheologic behavio(u)r of fracturing fluid.

Embodiment 7 is the broken glue test of the water adopting process sample containing the dust Control dissolved 200 °F.One purpose of this test determines that the sample of the dissolving that dust Control processes whether can the effect of adverse influence fracturing fluid breaker.In other words, this test attempts to find out whether chemical substance used in dust additive may require that more gel breaker is to reduce the viscosity of fracturing fluid or to change the speed that viscosity reduces in time.Water used in this test is prepared according to the same steps explained with embodiment 6.

Table 6

Result from the test carried out side by side shows similar viscosity profile, has from 7 minutes labellings until the closely similar value of last reading 20 minutes mark.Therefore, the test of this industry value demonstrates the coating processing chemical substance effect on the broken colloid system of test without impact.

Embodiment 8

In embodiment 8, the coating of the water-base emulsion of test 0.003wt% processes the ceramic proppant of 40/70, and described water-base emulsion comprises containing acrylate copolymer, C₆-C₁₂Ethoxylated alcohol and C₁₀-C₁₆The combination of the material of ethoxylated alcohol.This coating has three good effects: (1) its by pottery turbidity be reduced to 110 from 524NTU；(2) pottery dissolubility in the Fluohydric acid. of HCL and 3% of 12% is down to 2.6% from 3.4% by it；And (3) its K value is increased to 15 from 13.These results can not be foreseen based on the method for coating proppant.

This specification is not limited to described ad hoc approach, compositions or methodology, because these are likely to change.The term used in this manual is only for describing the purpose of specific version or embodiment, and is not intended to limit the scope of the embodiment described herein.Unless otherwise defined, otherwise all technology used herein and scientific terminology have the identical meanings that those skilled in the art are generally understood that.In some cases, having the term being generally understood that implication and be defined in this article, it is to know and/or for instant reference, and the introducing of these definition herein is not necessarily to be construed as expression and is different in essence in implication as commonly understood in the art.But, in case of a collision, with patent specification, it is as the criterion including definition.

Shall also be noted that unless clear stipulaties within a context, otherwise as in this article and singulative " (a) " used in the appended claims, " one (an) " and " this (the) " include plural form.

As used in this article, term " comprising (comprise) ", " there is (have) " and " including (include) " and as used in this article their change refer to " including but not limited to ".Although various compositionss, method and apparatus are described as " comprising " each ingredient or step (being interpreted as being meant that " including but not limited to "), but described compositions, method and apparatus can also is that substantially different by each ingredients and step form, or by each different ingredient and what step formed, and such term is appreciated that member's group that definition is substantially closed.

Disclosed herein various list of references and patent, purpose that each of which is cited for them and be incorporated herein by reference.

By foregoing, it will be appreciated that each embodiment of the present invention is described herein as purposes of illustration, and various amendment can be made when without departing substantially from scope and spirit of the present invention.Therefore, each embodiment disclosed herein is not intended to restrictive.

Claims

1. the method for processing free-pouring fine grained proppant solid, described method includes:

Making described solid contact with liquid treating agent less than 5 seconds, the amount of described liquid treating agent is kept substantially the free-flowing character of processed solid.

2. method according to claim 1, wherein said solid and described liquid treating agent contact more than once and each contact procedure less than 5 seconds.

3. method according to claim 1, wherein said fine grained proppant solid includes uncoated sand, have and solidify or the partially cured sand of coating, Alumina, pottery, the Alumina of coating or pottery.

4. the method according to any one of claim 1-3, wherein said fine grained proppant solid is uncoated sand or the sand of resin coating.

5. the method according to any one of claim 1-4, wherein said contact includes when described solid free-falling, directed free-falling time or in pneumatic conveying process, described liquid treating agent is sprayed on described proppant solid.

6. the method according to any one of claim 1-5, wherein said contact includes substantially simultaneously spraying described solid from more than one direction.

7. the method according to claim 1-6, wherein said liquid treating agent is effective for being coated with described solid with depositing dust coating.

8. the method according to any one of claim 1-7, wherein said liquid treating agent is for hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, or the coating comprising the ion exchange resin removing anion and/or halogen to be coated with described solid effective.

9. the method according to any one of claim 1-8, wherein said liquid treating agent comprises polysaccharide solution.

10. the method according to any one of claim 1-9, wherein said liquid treating agent comprises C₆-C₁₆Alcohol alcoxylates.

11. the method according to any one of claim 1-10, wherein said liquid treating agent comprises at least one acrylate copolymer.

12. the method according to any one of claim 1-11, wherein said liquid treating agent comprises acrylic copolymer.

13. the method according to any one of claim 1-8, wherein said liquid treating agent comprises at least one C₆-C₁₆The mixture of alcohol alcoxylates and at least one acrylate copolymer.

14. the method according to any one of claim 1-13, wherein based on the weight of described proppant solid, it is applied to the amount of described liquid treating agent of described solid less than Unit Weight 1wt%.

15. the method according to any one of claim 1-14, wherein said liquid treating agent is with the amount less than 0.5wt% and described solid contact.

16. the method according to any one of claim 1-14, wherein said liquid treating agent is with the amount less than 0.35wt% and described solid contact.

17. the method according to any one of claim 1-14, wherein said liquid treating agent is with the amount less than 0.25wt% and described solid contact.

18. the method according to any one of claim 1-17, wherein said liquid treating agent described solid by before static mixer immediately, when or afterwards immediately with described solid contact.

19. the method according to any one of claim 1-18, wherein said contact procedure includes:

With the first spray assembly, first liquid inorganic agent is applied on described solid in less than 5 seconds；

The solid making process passes through static mixer；And

With the second spray assembly, second liquid inorganic agent is applied on described solid in less than 5 seconds.

20. method according to claim 19, wherein said first liquid inorganic agent and second liquid inorganic agent are different solution.

21. the method according to claim 19 or 20, wherein said second liquid inorganic agent is applied to described solid at described solid immediately by after described static mixer.

22. the method according to any one of claim 19-21, at least one in wherein said first and second liquid treating agents is effective for being coated with described solid with depositing dust coating.

23. the method according to any one of claim 19-22, at least one in wherein said first and second liquid treating agents is effective for being coated with described solid with additional coatings.

24. method according to claim 23, wherein said additional coatings is hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise the coating of the ion exchange resin removing anion and/or halogen.

25. method according to claim 1, wherein said solid contacts less than 2 seconds with described liquid treating agent.

26. method according to claim 1, wherein said solid contacts less than 1 second with described liquid treating agent.

27. method according to claim 1, wherein said solid contacts the distance elapsed time of 4 feet, described solid whereabouts with described liquid treating agent.

28. for the method producing the free-pouring fine grained proppant solid with depositing dust performance, described method includes:

Making described solid contact with depositing dust liquid treating agent less than 5 seconds, the amount of described depositing dust liquid treating agent is kept substantially the free-flowing character of processed solid and reduces the dust produced by described solid.

29. method according to claim 28, the dust wherein produced by the free-pouring fine grained proppant solid with depositing dust performance is less than the dust produced by the solid not contacted with depositing dust liquid treating agent.

30. the method according to claim 28 or 29, wherein said liquid treating agent is for hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, or the coating comprising the ion exchange resin removing anion and/or halogen to be coated with described solid effective.

31. the method according to any one of claim 28-30, wherein said liquid treating agent comprises polysaccharide solution.

32. the method according to any one of claim 28-31, wherein said liquid treating agent comprises C₆-C₁₆Alcohol alcoxylates.

33. the method according to any one of claim 28-32, wherein said liquid treating agent comprises at least one acrylate copolymer.

34. the method according to any one of claim 28-30, wherein said liquid treating agent comprises acrylic copolymer.

35. according to the method according to any one of claim 28-30 or 34, wherein said liquid treating agent comprises at least one C₆-C₁₆The mixture of alcohol alcoxylates and at least one acrylate copolymer.

36. the method according to any one of claim 28-35, wherein based on the weight of described proppant solid, it is applied to the amount of described liquid treating agent of described solid less than Unit Weight 1wt%.

37. the method according to any one of claim 28-35, wherein said liquid treating agent is with the amount less than 0.5wt% and described solid contact.

38. the method according to any one of claim 28-35, wherein said liquid treating agent is with the amount less than 0.35wt% and described solid contact.

39. the method according to any one of claim 28-35, wherein said liquid treating agent is with the amount less than 0.25wt% and described solid contact.

40. the method according to any one of claim 28-30, wherein said liquid treating agent comprises C ethoxylation, propenoxylated₆-C₁₂Alcohol, C ethoxylation, propenoxylated₁₀-C₁₆The emulsion of alcohol, acrylate copolymer and water；About 15% to about 30%, about 17% to about 28% or about 20% to about 25% ethoxylation, propenoxylated C₆-C₁₂Alcohol, or about 5% to about 20%, about 8% to about 18% or about 10% to about 15% ethoxylation, propenoxylated C₁₀-C₁₆Alcohol；Or the ethoxylation of about 20% to about 25%, propenoxylated C₆-C₁₂Alcohol, the C ethoxylation of about 10% to about 15%, propenoxylated₁₀-C₁₆Alcohol, the acrylate copolymer of about 5% to about 10%, the ammonia less than 0.1% and the free monomer less than 0.05%；Or the ethoxylation of about 20% to about 25%, propenoxylated C₆-C₁₂Alcohol, the C ethoxylation of about 10% to about 15%, propenoxylated₁₀-C₁₆Alcohol, the acrylate copolymer of about 5% to about 10%, the ammonia less than 0.1%, the free monomer less than 0.05%, remaining for water.

41. for the method being coated with free-pouring proppant, described method includes:

Making described proppant contact with liquid treating agent less than 5 seconds to produce the free-pouring proppant of coating, the amount of described liquid treating agent is kept substantially the free-flowing character of proppant,

Wherein said coating is depositing dust coating, hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, or comprise the coating of the ion exchange resin removing anion and/or halogen, or its combination in any.

42. method according to claim 41, wherein said coating is depositing dust coating.

43. the method according to claim 41 or 42, wherein said coating is hydrophobic coating, reduce the coating of friction, the coating comprising tracer, impact modifying agent coating, for time delay or stage by stage release additives coating, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, enhancing proppant resistance to crushing coating, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation or comprise coating or its combination in any of the ion exchange resin removing anion and/or halogen.

44. a free-pouring proppant for coating, it comprises coating that is dry and/or that solidify, and coating that is described dry and/or that solidify comprises the inorganic agent less than about 3wt%.

45. the free-pouring proppant of coating according to claim 44, the free-pouring proppant of wherein said coating presents airborne dust compared with uncoated proppant and generates minimizing.

46. the free-pouring proppant of the coating according to any one of claim 44 or 45, it comprises the described coating of 0.0009-0.5wt%.

47. the free-flow proppant of the coating according to any one of claim 44 or 45, it comprises the described coating of 0.001-0.35wt%.

48. the free-flow proppant of the coating according to any one of claim 44-47, wherein said coating comprises following one or more: monosaccharide or polysaccharide, surfactant, alcohol alcoxylates, acrylate copolymer, methacrylate polymer, acrylic acid and/or methacrylic acid copolymer, methacrylate and its copolymer, polyvinyl acetate, ethylene acrylic acid co polymer, polybutadiene, low-molecular-weight mineral oil, acrylamide polymer, lignosulfonates, water dispersible natural gum, water-dispersible pectin, water dispersible starch derivant, water-dispersible fiber element derivant, or its any mixture.

49. the free-flow proppant of the coating according to any one of claim 45-48, wherein said coating comprises one or more monosaccharide or polysaccharide.

50. the free-flow proppant of the coating according to any one of claim 44-49, wherein said coating comprises one or more alcohol alcoxylates.

51. the free-flow proppant of the coating according to any one of claim 44-50, wherein said coating comprises at least one C₆-C₁₂Alcohol alcoxylates and at least one C₁₀-C₁₆Alcohol alcoxylates.

52. the free-flow proppant of the coating according to any one of claim 44-51, wherein said coating comprises one or more acrylate copolymers.

53. the free-flow proppant of the coating according to any one of claim 44-52, wherein said coating comprises at least one C₆-C₁₂Alcohol alcoxylates, at least one C₁₀-C₁₆Alcohol alcoxylates and at least one acrylate copolymer.

54. the free-flow proppant of the coating according to any one of claim 44-48, wherein said coating comprises one or more methacrylate polymers, one or more acrylic acid and/or methacrylic acid copolymer and one or more methacrylates.

55. the free-flow proppant of the coating according to any one of claim 44-54, wherein said coating includes hydrophobic coating, reduce the coating of friction, comprise the coating of tracer, impact modifying agent coating, coating for time delay or release additives stage by stage, control the coating of sulfide, different polymer coatings, acidproof or alkaline-resisting coating, corrosion-inhibiting coating, strengthen the coating of proppant resistance to crushing, suppress the coating of paraffin precipitation or gathering, suppress the coating of asphaltene precipitation, or comprise the coating of the ion exchange resin removing anion and/or halogen.

56. the free-flow proppant of the coating according to any one of claim 44-54, wherein said coating also comprises sulfide scavanger or antisludging agent.