CN104152136B - Method for preparing ultra-low-density fracturing and propping agent by using white clay - Google Patents

Method for preparing ultra-low-density fracturing and propping agent by using white clay Download PDF

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CN104152136B
CN104152136B CN201410436124.4A CN201410436124A CN104152136B CN 104152136 B CN104152136 B CN 104152136B CN 201410436124 A CN201410436124 A CN 201410436124A CN 104152136 B CN104152136 B CN 104152136B
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white clay
agent
extremely
low density
reaction
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CN104152136A (en
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严春杰
陈宇婷
陈涛
王义霞
公衍生
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China University of Geosciences
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/80Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open

Abstract

The invention discloses a method for preparing an ultra low density fracturing and propping agent by using white clay. The method comprises the following steps: firstly, taking the white clay and a coupling agent, dispersing the white clay and the coupling agent into toluene, stirring the white clay, the coupling agent and the toluene, and after a reaction is completed, sucking, filtering and drying the white clay, the coupling agent and the toluene which are stirred to obtain modified white clay, wherein the white clay is fly ash extracted aluminum residues, and the added quantity of the coupling agent is 1-5wt% of the white clay; using water as a disperse medium, adding a dispersing agent and then adding the modified white clay, dripping monomer solutions in which a cross linking agent and an initiating agent are dissolved, performing a polyreaction, and filtering, cleaning and drying reactants to obtain an ultra-low-density petroleum fracturing and propping agent. The density of the propping agent prepared by the method disclosed by the invention is 1.08-1.25g/cm3 and is close to the density of the water, in the use process, saline water can be used as sand carrying liquid, the compressive strength of the propping agent is high, and the largest crushing rate under 52Mpa is only 3.65%, so that the propping agent is suitable for fracturing of a deep well. In addition, the preparation technology is simple, the propping agent can be used for industrial grade production, the fracturing construction cost is greatly reduced, and the increase in the oil production of petroleum is facilitated.

Description

A kind of method preparing extremely-low density fracturing propping agents using white clay
Technical field
The invention belongs to pressure break oil recovery technique field is and in particular to one kind prepares extremely-low density fracturing propping agents using white clay Method.
Background technology
Fracturing propping agents are to support the crack producing in Oil/gas Well hydraulic fracturing process, strengthening the water conservancy diversion energy on stratum Power, improves oil, the yield of gas and a kind of wide variety of solid particle.Preferably proppant should have the characteristics that:(1) strong Degree is high, will not be crushed for heavy duty service;(2) relative density is little, is easy to pump into underground;(3) chemical inertness is good, can resist ground In layer, the erosion of water body, equally stable at high temperature;(4) sphericity is good, to keep preferable space between proppant particles.
Existing proppant is broadly divided into three types.Oil fracturing ceramsite propping agent is prepared with raw mineral materials such as bauxites Development existing many documents and patent report.Haydite class proppant not only expensive it is often more important that due to relative density Greatly, the viscosity requiring load fluid in construction must be very high, and this high viscosity load fluid is usually organic polymer solution (example As:Guanidine glue), pressure break energy consumption is big, high cost and pollute environment and destroy in-place permeability.
Equations of The Second Kind proppant is mainly some natural materials such as quartz sand (US patent 5,420,174 to Deprawshad et al;US patent 5,218,038 to Johnson et al and US patent 5,639,806 to Johnson et al:EP patent No.0542397).This kind of proppant is cheap and easily-available, and relative density is about in 2.5. In shallow well, application quartz sand has certain success rate for proppant.But because of sand insufficient strength, (pressure when starting broken is about For 25MPa), in the case that closure stress is higher, will crush, produce substantial amounts of fragment and fine silt.These fine silts exist Migrate in crack and block crack, thus reducing the flow conductivity in crack.In hydraulic fracturing job, using such Support agent also has a unsurmountable shortcoming, and that is, they all can embed stratum or occur when Oil/gas Well puts into production proppant anti- Tell or crack emptying phenomenon.
3rd class is organic resin application type proppant.These resins mainly include epoxy resin, furan, phenolic resin or Their mixture.The content of resin is usually to be applied the 1-8% of particle weight, and particulate matter can be sand, haydite, pulverizing The walnut shell crossed or other particulate matters.Chinese patent 200710188410 disclose " preparation method of low-density propping agent and Preparation technology ", Chinese patent 201010278084 discloses " a kind of fiber composite sand control material and preparation method thereof ", respectively profit With Plant fiber or fibrous material as raw material, in organic curing non-sintered molding or incorporation fracturing fluid, play sand prevention Oil Guide Effect, and there is relatively low density, they only need in use can as fracturing fluid with tap water or saline To meet the requirement of pressure break oil recovery, this kind of proppant is referred to as extremely-low density fracturing propping agents.But this kind of proppant often has by force The low defect with temperature tolerance difference and high cost of degree.
Thus, research and develop a kind of high intensity, low-density, low cost fracturing propping agents, for improve China's oil and gas production and Grade is most important;Additionally, being applied in pressure break oil recovery technique, secondary environmental pollution will not be brought and reduce Its cost of manufacture, will have obvious environment demonstration benefit and economic benefit, and meet China's strategy of sustainable development requirement.
Content of the invention
The present invention is intended to provide a kind of intensity is high, density is low, the preparation side of low cost, process is simple fracturing propping agents Method.
For reaching above-mentioned purpose, as follows using technical scheme:
A kind of method preparing extremely-low density fracturing propping agents using white clay, comprises the following steps:
1) white clay, coupling agent is taken to be scattered in stirring in toluene, reaction terminates rear sucking filtration, drying, obtains modified white clay;Described white Mud is residue of aluminum-extracted pulverized fuel ash;Coupling agent addition is the 1-5wt% of white clay;
2) with water as disperse medium, add modified white clay after adding dispersant, then Deca is dissolved with cross-linking agent and initiator Monomer solution carry out polyreaction, filter, washing, dry and obtain extremely-low density petroleum fracturing propping agent;Wherein, polyreaction Water in mass ratio:Dispersant:White clay:Monomer:Cross-linking agent:Initiator=140:0.4~1.2:2~6:15~30:3.0~5.0: 0.25~0.45 is carried out.
By such scheme, described coupling agent is silane coupler or aluminate coupling agent.
By such scheme, described dispersant is Mg (OH)2.
By such scheme, described cross-linking agent is divinylbenzene or cyclopentadiene.
By such scheme, described initiator is benzoyl peroxide.
By such scheme, at 60 DEG C of described polyreaction, add dispersant, monomer solution is warmed up to 75-80 DEG C after dripping Reaction 0.5-1h, 1-2h, 90-95 DEG C of reaction 1h of 85 DEG C of reactions terminate.
White clay is a kind of thermal power plant waste coal ash residue of aluminum-extracted, and main component is Si and Al, with most of nothing Machine mineralogical composition is close, can be used for building block, brickmaking, the low-grade concrete of system.But greatly still it is used for filling out hole, paving Road, it is made a low multiple use, and governments at all levels all take much count of the process problem of white clay, but there is presently no more preferable Application way. The technical scheme is that with modified white clay as inorganic additive, the method system that MMA adopts suspension polymerisation for organic monomer Standby compound proppant.The low-density of the existing high molecular polymer of proppant being so obtained and high tenacity, and organic/inorganic substance Intensity and temperature tolerance, and white clay and macromolecular chain PMMA interaction, the motion hindering polymer macromolecule chain is thus improve Overall temperature tolerance and comprcssive strength.
Beneficial effects of the present invention:
By add in high molecular polymer building-up process a certain amount of modification white clay can reach raising polymer strong Degree and durothermic purpose, thus in being applied to, deep well fracturing uses, and is the product that Petroleum Industry creates more high-quality.
The proppant density prepared is 1.08~1.25g/cm3, density, close to water, can use salt in use Water serves as load fluid, such that it is able to pressing crack construction cost is greatly reduced, and reduce avoid using the pluronic polymers such as guanidine glue drop The low pollution to environment.
Both increased utilization rate and the added value of white clay, reduce the preparation cost of extremely-low density fracturing propping agents.And make Standby process is simple is suitable to industrialized production.
Specific embodiment
Following examples explain technical scheme further, but not as limiting the scope of the invention.
The method that the present invention prepares extremely-low density fracturing propping agents using white clay, comprises the following steps:
1) white clay, coupling agent is taken to be scattered in stirring in toluene, reaction terminates rear sucking filtration, drying, obtains modified white clay;Described white Mud is residue of aluminum-extracted pulverized fuel ash;Coupling agent addition is the 1-5wt% of white clay;
2) with water as disperse medium, add modified white clay after adding dispersant, then Deca is dissolved with cross-linking agent and initiator Monomer solution carry out polyreaction, filter, washing, dry and obtain extremely-low density petroleum fracturing propping agent;Wherein, polyreaction Water in mass ratio:Dispersant:White clay:Monomer:Cross-linking agent:Initiator=140:0.4~1.2:2~6:15~30:3.0~5.0: 0.25~0.45 is carried out.
Wherein, coupling agent is chosen as silane coupler (KH-570, KH-550 series) or aluminate coupling agent.
Dispersant selects Mg (OH)2.
Initiator selects benzoyl peroxide.
Optimally, add dispersant at 60 DEG C of polyreaction, monomer solution is warmed up to 75-80 DEG C of reaction 0.5- after dripping 1h, 1-2h, 90-95 DEG C of reaction 1h of 85 DEG C of reactions terminate.
By add in high molecular polymer building-up process a certain amount of modification white clay can reach raising polymer strong Degree and durothermic purpose.The proppant density prepared is 1.08~1.25g/cm3, density, close to water, using process In can serve as load fluid with saline, such that it is able to pressing crack construction cost is greatly reduced, and reduce avoid contour using guanidine glue Molecule auxiliary agent reduces the pollution to environment.
Embodiment 1
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH570 are mixed, warming-in-water to 90 DEG C of magnetic agitation 6h, reaction knot Shu Hou, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, drying modified white clay at 75 DEG C.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/LMgCl is added in container2Solution is (anti- Magnesium hydroxide dispersant should be obtained), warming-in-water to 60 DEG C of mechanical agitation, add 2g modified white clay immediately, then by 20g methyl It is added dropwise to container after acrylic acid methyl ester., 3g divinylbenzene (DVB), 0.35g initiator (BPO) stirring and evenly mixing, adjust rotating speed 250r/ Min, be warmed up to 80 DEG C reaction 0.5h, 85 DEG C reaction 1h, 90 DEG C reaction 1h, stopped reaction sucking filtration, with distilled water wash several times, 70 DEG C dry, crossing 10-60 mesh sieve, to obtain polymethyl methacrylate composite balls is extremely-low density petroleum fracturing propping agent.
Embodiment 2
The modification of white clay:
100ml toluene solution, 50g white clay and 2g KH550 are mixed, warming-in-water to 95 DEG C of magnetic agitation 5h, reaction knot Shu Hou, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, drying modified white clay at 75 DEG C.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl is added in container2Solution, water Bath is warmed up to 60 DEG C of mechanical agitation, adds 4g modified white clay immediately, then by 20g methyl methacrylate, 3g DVB, 0.35g It is added dropwise to container after BPO stirring and evenly mixing, adjusts rotating speed 280r/min, be warmed up to 75 DEG C of reaction 1h, 85 DEG C of reaction 1h, 90 DEG C of reactions 1h, stopped reaction sucking filtration, with distilled water wash several times, and 70 DEG C of drying, cross 10-60 mesh sieve and obtain polymethyl methacrylate composite balls I.e. extremely-low density petroleum fracturing propping agent.
Embodiment 3
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH570 are mixed, warming-in-water to 100 DEG C of magnetic agitation 4h, reaction After end, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, at 75 DEG C, drying is modified white Mud.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl is added in container2Solution, Warming-in-water to 60 DEG C of mechanical agitation, adds 6g modified white clay immediately, then by 20g methyl methacrylate, 3g DVB, It is added dropwise to container after 0.35gBPO stirring and evenly mixing, adjusts rotating speed 300r/min, be warmed up to 80 DEG C of reaction 1h, 85 DEG C of reaction 2h, 90 DEG C reaction 1h, stopped reaction sucking filtration, with distilled water wash several times, 70 DEG C drying, cross 10-60 mesh sieve obtain polymethyl methacrylate Composite balls are extremely-low density petroleum fracturing propping agent.
Embodiment 4
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH570 are mixed, warming-in-water to 105 DEG C of magnetic agitation 3h, reaction After end, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, at 75 DEG C, drying is modified white Mud.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl is added in container2Solution, Warming-in-water to 60 DEG C of mechanical agitation, adds 4g modified white clay immediately, then by 20g methyl methacrylate, 3gDVB, It is added dropwise to container after 0.35gBPO stirring and evenly mixing, adjusts rotating speed 270r/min, be warmed up to 75 DEG C of reaction 1h, 85 DEG C of reaction 2h, 95 DEG C reaction 1h, stopped reaction sucking filtration, with distilled water wash several times, 70 DEG C drying, cross 10-60 mesh sieve obtain polymethyl methacrylate Composite balls are extremely-low density petroleum fracturing propping agent.
Embodiment 5
The modification of white clay:
100ml toluene solution, 50g white clay and 2g aluminate coupling agent are mixed, warming-in-water is to 110 DEG C of magnetic agitation 2h, reaction terminate after, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, drying at 75 DEG C Modified white clay.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl is added in container2Solution, Warming-in-water to 60 DEG C of mechanical agitation, adds 2g modified white clay immediately, then by 20g methyl methacrylate, 3g DVB, It is added dropwise to container after 0.35gBPO stirring and evenly mixing, adjusts rotating speed 260r/min, be warmed up to 80 DEG C of reaction 0.5h, 85 DEG C of reaction 2h, 90 DEG C of reaction 1h, stopped reaction sucking filtration, with distilled water wash several times, and 70 DEG C of drying, cross 10-60 mesh sieve and obtain poly-methyl methacrylate Ester composite balls are extremely-low density petroleum fracturing propping agent.
Embodiment 6
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH550 are mixed, warming-in-water to 100 DEG C of magnetic agitation 4h, reaction After end, with toluene (with after toluene solution can directly reclaim reuse) wash 1 time, at 75 DEG C, drying is modified white Mud.
The preparation of extremely-low density fracturing propping agents:
140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl is added in container2Solution, Warming-in-water to 60 DEG C of mechanical agitation, adds 2g modified white clay immediately, then by 20g methyl methacrylate, 3gDVB, It is added dropwise to container after 0.35gBPO stirring and evenly mixing, adjusts rotating speed 300r/min, be warmed up to 80 DEG C of reaction 0.5h, 85 DEG C of reaction 1h, 90 DEG C of reaction 1h, stopped reaction sucking filtration, with distilled water wash several times, and 70 DEG C of drying, cross 10-60 mesh sieve and obtain poly-methyl methacrylate Ester composite balls are extremely-low density petroleum fracturing propping agent.
Main performance index of the present invention and assay method:
Above the bulk density of prepared poly (methyl methacrylate) micro-sphere, apparent density, sphericity, percentage of damage and The test of flow conductivity is all according to People's Republic of China (PRC) oil and gas industry standard SY/T 5108-2006《Fracturing propping agents And performance indications and test recommendation method》.The results are shown in Table 1.
Table 1. low-density petroleum fracturing propping agent embodiment test performance
As can be seen from Table 1:Proppant density of the present invention is 1.08~1.25g/cm3, density, close to water, using Load fluid can be served as with saline, its comprcssive strength is high, under 52Mpa, maximum percentage of damage is only 3.65% it is adaptable to deep-well in journey Pressure break.
The preparation process is simple of the extremely-low density high-strength pressure crack proppant of the present invention, can be used for technical grade and produces, greatly Amplitude reduction pressing crack construction cost, is conducive to the raising of oil oil production.
Finally to be described, above example is merely to illustrate technical scheme rather than the present invention is protected The restriction of scope, although being explained in detail to the present invention with reference to preferred embodiment, those of ordinary skill in the art should manage Solution, technical scheme can be modified or equivalent, without deviating from technical solution of the present invention essence and Scope.

Claims (6)

1. a kind of prepare the method for extremely-low density fracturing propping agents it is characterised in that comprising the following steps using white clay:
1) white clay, coupling agent is taken to be scattered in stirring in toluene, reaction terminates rear sucking filtration, drying, obtains modified white clay;Described white clay is Residue of aluminum-extracted pulverized fuel ash;Coupling agent addition is the 1-5wt% of white clay;
2) with water as disperse medium, add modified white clay after adding dispersant, then Deca is dissolved with the first of cross-linking agent and initiator Base methyl acrylate solution carries out polyreaction, filters, washs, drying obtains extremely-low density petroleum fracturing propping agent;Wherein, gather Close reaction water in mass ratio:Dispersant:White clay:Methyl methacrylate:Cross-linking agent:Initiator=140:0.4~1.2:2~6: 15~30:3.0~5.0:0.25~0.45 is carried out.
2. as claimed in claim 1 prepare the method for extremely-low density fracturing propping agents it is characterised in that described coupling using white clay Agent is silane coupler or aluminate coupling agent.
3. as claimed in claim 1 prepare the method for extremely-low density fracturing propping agents it is characterised in that described dispersion using white clay Agent is Mg (OH)2.
4. as claimed in claim 1 prepare the method for extremely-low density fracturing propping agents it is characterised in that described crosslinking using white clay Agent is divinylbenzene or cyclopentadiene.
5. as claimed in claim 1 prepare the method for extremely-low density fracturing propping agents it is characterised in that described initiation using white clay Agent is benzoyl peroxide.
6. as claimed in claim 1 prepare the method for extremely-low density fracturing propping agents it is characterised in that described polymerization using white clay Add dispersant at 60 DEG C of reaction, methyl methacrylate solution be warmed up to after dripping 75-80 DEG C of reaction 0.5-1h, 85 DEG C anti- 1-2h, 90-95 DEG C of reaction 1h is answered to terminate.
CN201410436124.4A 2014-08-29 2014-08-29 Method for preparing ultra-low-density fracturing and propping agent by using white clay Expired - Fee Related CN104152136B (en)

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CN107954680A (en) * 2016-10-18 2018-04-24 中国石油化工股份有限公司 A kind of high-temperature chlorine oxygen magnesium thermosetting resin gelling system and firming body and its preparation method
CN106833601A (en) * 2017-01-17 2017-06-13 中国地质大学(武汉) Modified super-low-density proppant of a kind of Graphene and preparation method thereof

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