CN104152136A - 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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CN104152136A
CN104152136A CN201410436124.4A CN201410436124A CN104152136A CN 104152136 A CN104152136 A CN 104152136A CN 201410436124 A CN201410436124 A CN 201410436124A CN 104152136 A CN104152136 A CN 104152136A
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white clay
agent
low density
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coupling agent
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CN104152136B (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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    • 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
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    • 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
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    • 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
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    • 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

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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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 of utilizing white clay to prepare extremely-low density fracturing propping agents
Technical field
The invention belongs to pressure break oil recovery technique field, be specifically related to a kind of method of utilizing white clay to prepare extremely-low density fracturing propping agents.
Background technology
Fracturing propping agents are the cracks that produce in supporting oil gas well waterfrac treatment process, strengthen the flow conductivity on stratum, improve the output of oil, gas and a kind of solid particulate of widespread use.Desirable propping agent should have following characteristics: (1) intensity is high, can be not crushed for heavy duty service; (2) relative density is little, is convenient to pump into underground; (3) unreactiveness is good, can resist the erosion of water body in stratum, at high temperature stable equally; (4) degree of sphericity is good, to keep good space between proppant particles.
Existing propping agent is mainly divided into three types.The existing many documents of development and the patent report of with raw mineral materialss such as bauxitic clays, preparing oil fracturing ceramsite propping agent.Haydite class propping agent is not only expensive, the more important thing is because relative density is large, in construction, require the viscosity of sand-carrying agent must be very high, for example, and this high viscosity sand-carrying agent (: guanidine glue), pressure break energy consumption is large, cost is high and contaminate environment and destruction zone permeability is generally organic polymer solution.
Equations of The Second Kind propping agent is mainly that some crude substance are 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 class propping agent is cheaply easy to get, and relative density is about that in 2.5., to apply quartz sand in shallow well be that propping agent has certain success ratio.But because of sand insufficient strength (pressure while starting fragmentation is about 25MPa), in the situation that closure stress is higher, will be broken, produce a large amount of fragments and fine silt.These fine silts move and stop up crack in crack, thereby reduce the flow conductivity in crack.In waterfrac treatment operation, use such propping agent to also have a unsurmountable shortcoming, they all can embed stratum or when Oil/gas Well puts into production, occur that propping agent is counter to be told or the emptying phenomenon in crack.
The 3rd class is organic resin application type propping agent.These resins mainly comprise epoxy resin, furans, resol or their mixture.The content of resin is generally the 1-8% of coated particle weight, and particulate matter can be nut-shell or other particulate matter of sand, haydite, pulverizing.Chinese patent 200710188410 discloses " 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 ", utilize respectively vegetable fibre or filamentary material as raw material, organicly solidify non-sintered moulding or mix the effect of playing sand prevention Oil Guide in fracturing liquid, and there is lower density, they in use only need to just can meet as fracturing liquid the requirement that pressure break is recovered the oil with tap water or salt solution, and this class propping agent is called extremely-low density fracturing propping agents.But this class propping agent often has the defect that intensity is low He temperature tolerance is poor and cost is high.
Thus, research and develop a kind of high strength, low density, fracturing propping agents cheaply, for improving, China's oil and gas production and grade are most important; In addition, be applied in pressure break oil recovery technique, can not bring secondary environmental pollution and reduce its cost of manufacture, will there is obvious environment demonstration benefit and economic benefit, and meet China's strategy of sustainable development requirement.
Summary of the invention
The present invention aims to provide that a kind of intensity is high, density is low, cost is low, the preparation method of the simple fracturing propping agents of technique.
For achieving the above object, adopt technical scheme as follows:
Utilize white clay to prepare a method for extremely-low density fracturing propping agents, comprise the following steps:
1) get white clay, coupling agent is scattered in toluene and stirs, reaction finish rear suction filtration, oven dry, obtain modified white clay; Described white clay is residue of aluminum-extracted pulverized fuel ash; Coupling agent add-on is the 1-5wt% of white clay;
2) take water as dispersion medium, add modified white clay after adding dispersion agent, then drip the monomer solution that is dissolved with linking agent and initiator and carry out polyreaction, filter, washing, dry and obtain extremely-low density petroleum fracturing propping agent; Wherein, polyreaction water in mass ratio: dispersion agent: white clay: monomer: linking agent: carry out initiator=140:0.4~1.2:2~6:15~30:3.0~5.0:0.25~0.45.
Press such scheme, described coupling agent is silane coupling agent or aluminate coupling agent.
Press such scheme, described dispersion agent is Mg (OH) 2.
Press such scheme, described linking agent is divinylbenzene or cyclopentadiene.
Press such scheme, described initiator is benzoyl peroxide.
Press such scheme, at 60 ℃ of described polyreactions, add dispersion agent, after monomer solution drips, be warmed up to 75-80 ℃ of reaction 0.5-1h, 1-2h, 90-95 ℃ of reaction 1h of 85 ℃ of reactions finishes.
White clay is a kind of fuel-burning power plant waste residue of aluminum-extracted pulverized fuel ash, and main component is Si and Al, close with most of inorganic mineral composition, can be used for building block, and brickmaking, makes low-grade concrete.But greatly still for filling out hole, paving the way, it is made a low multiple use, and governments at all levels all take much count of the processing problem of white clay, but also there is no at present better utilised method.Technical scheme of the present invention is that to take the white clay of modification be inorganic additives, and MMA is that organic monomer adopts the method for suspension polymerization to prepare compound propping agent.Low density and the high tenacity of the existing high molecular polymer of propping agent making like this, the intensity of organic/inorganic substance and temperature tolerance again, and white clay and macromolecular chain PMMA interact, thereby the motion of obstruction polymer macromolecule chain improves whole temperature tolerance and ultimate compression strength.
Beneficial effect of the present invention:
By add the white clay of a certain amount of modification in high molecular polymer building-up process, can reach and improve polymer strength and durothermic object, thereby in being applicable to, deep well fracturing uses, for Petroleum Industry has been created the more product of high-quality.
The propping agent density of preparing is 1.08~1.25g/cm 3, density, close to water, in use can be served as sand-carrying agent with salt solution, thereby can significantly reduce pressing crack construction cost, and reduces and avoid using the pluronic polymers such as guanidine glue to reduce the pollution to environment.
Both increase utilization ratio and the added value of white clay, reduced the preparation cost of extremely-low density fracturing propping agents.And preparation technology is simply suitable for suitability for industrialized production.
Embodiment
Following examples are explaination technical scheme of the present invention further, but not as limiting the scope of the invention.
The present invention utilizes white clay to prepare the method for extremely-low density fracturing propping agents, comprises the following steps:
1) get white clay, coupling agent is scattered in toluene and stirs, reaction finish rear suction filtration, oven dry, obtain modified white clay; Described white clay is residue of aluminum-extracted pulverized fuel ash; Coupling agent add-on is the 1-5wt% of white clay;
2) take water as dispersion medium, add modified white clay after adding dispersion agent, then drip the monomer solution that is dissolved with linking agent and initiator and carry out polyreaction, filter, washing, dry and obtain extremely-low density petroleum fracturing propping agent; Wherein, polyreaction water in mass ratio: dispersion agent: white clay: monomer: linking agent: carry out initiator=140:0.4~1.2:2~6:15~30:3.0~5.0:0.25~0.45.
Wherein, coupling agent is chosen as silane coupling agent (KH-570, KH-550 series) or aluminate coupling agent.
Dispersion agent is selected Mg (OH) 2.
Initiator is selected benzoyl peroxide.
Optimally, at 60 ℃ of polyreactions, add dispersion agent, after monomer solution drips, be warmed up to 75-80 ℃ of reaction 0.5-1h, 1-2h, 90-95 ℃ of reaction 1h of 85 ℃ of reactions finishes.
By add the white clay of a certain amount of modification in high molecular polymer building-up process, can reach raising polymer strength and durothermic object.The propping agent density of preparing is 1.08~1.25g/cm 3, density, close to water, in use can be served as sand-carrying agent with salt solution, thereby can significantly reduce pressing crack construction cost, and reduces and avoid using the pluronic polymers such as guanidine glue to reduce 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 ℃ magnetic agitation 6h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/LMgCl 2solution (reaction obtains magnesium hydroxide dispersion agent), warming-in-water to 60 ℃ mechanical stirring, add immediately 2g modified white clay, then will after 20g methyl methacrylate, 3g divinylbenzene (DVB), 0.35g initiator (BPO) stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 250r/min, be warmed up to 80 ℃ of reaction 0.5h, 85 ℃ of reaction 1h, 90 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Embodiment 2
The modification of white clay:
100ml toluene solution, 50g white clay and 2g KH550 are mixed, warming-in-water to 95 ℃ magnetic agitation 5h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl 2solution, warming-in-water to 60 ℃ mechanical stirring, adds 4g modified white clay immediately, then will after 20g methyl methacrylate, 3g DVB, 0.35g BPO stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 280r/min, be warmed up to 75 ℃ of reaction 1h, 85 ℃ of reaction 1h, 90 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Embodiment 3
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH570 are mixed, warming-in-water to 100 ℃ magnetic agitation 4h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl 2solution, warming-in-water to 60 ℃ mechanical stirring, adds 6g modified white clay immediately, then will after 20g methyl methacrylate, 3g DVB, 0.35gBPO stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 300r/min, be warmed up to 80 ℃ of reaction 1h, 85 ℃ of reaction 2h, 90 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Embodiment 4
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH570 are mixed, warming-in-water to 105 ℃ magnetic agitation 3h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl 2solution, warming-in-water to 60 ℃ mechanical stirring, adds 4g modified white clay immediately, then will after 20g methyl methacrylate, 3gDVB, 0.35gBPO stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 270r/min, be warmed up to 75 ℃ of reaction 1h, 85 ℃ of reaction 2h, 95 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Embodiment 5
The modification of white clay:
100ml toluene solution, 50g white clay and 2g aluminate coupling agent are mixed, warming-in-water to 110 ℃ magnetic agitation 2h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl 2solution, warming-in-water to 60 ℃ mechanical stirring, adds 2g modified white clay immediately, then will after 20g methyl methacrylate, 3g DVB, 0.35gBPO stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 260r/min, be warmed up to 80 ℃ of reaction 0.5h, 85 ℃ of reaction 2h, 90 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Embodiment 6
The modification of white clay:
100ml toluene solution, 50g white clay and 1g KH550 are mixed, warming-in-water to 100 ℃ magnetic agitation 4h, after reaction finishes, with toluene (with after toluene solution can directly reclaim and reuse) wash 1 time, dry and obtain modified white clay at 75 ℃.
The preparation of extremely-low density fracturing propping agents:
In container, add 140ml distilled water, 10ml NaOH (2mol/L) solution and 10ml 1mol/L MgCl 2solution, warming-in-water to 60 ℃ mechanical stirring, adds 2g modified white clay immediately, then will after 20g methyl methacrylate, 3gDVB, 0.35gBPO stirring and evenly mixing, be added dropwise to container, adjusting rotary speed 300r/min, be warmed up to 80 ℃ of reaction 0.5h, 85 ℃ of reaction 1h, 90 ℃ of reaction 1h, stopped reaction suction filtration, with distilled water wash several times, 70 ℃ of oven dry, it is extremely-low density petroleum fracturing propping agent that mistake 10-60 mesh sieve obtains polymethylmethacrylate compound ball.
Main performance index of the present invention and measuring method:
The test of the volume density of prepared poly (methyl methacrylate) micro-sphere, volume density, degree of sphericity, percentage of damage and flow conductivity is all according to People's Republic of China's oil and gas industry standard SY/T 5108-2006 < < fracturing propping agents and performance index and test recommend method > > above.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: propping agent density of the present invention is 1.08~1.25g/cm 3, density, close to water, in use can be served as sand-carrying agent with salt solution, and its ultimate compression strength is high, and under 52Mpa, maximum percentage of damage is only 3.65%, is applicable to deep well fracturing.
The preparation technology of extremely-low density high-strength pressure crack proppant of the present invention is simple, can produce for technical grade, significantly reduces pressing crack construction cost, is conducive to the raising of oil oil offtake.
Last institute is noted that; above embodiment is only for illustrating technical scheme of the present invention but not limiting the scope of the invention; although the present invention is explained in detail with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.

Claims (6)

1. utilize white clay to prepare a method for extremely-low density fracturing propping agents, it is characterized in that comprising the following steps:
1) get white clay, coupling agent is scattered in toluene and stirs, reaction finish rear suction filtration, oven dry, obtain modified white clay; Described white clay is residue of aluminum-extracted pulverized fuel ash; Coupling agent add-on is the 1-5wt% of white clay;
2) take water as dispersion medium, add modified white clay after adding dispersion agent, then drip the monomer solution that is dissolved with linking agent and initiator and carry out polyreaction, filter, washing, dry and obtain extremely-low density petroleum fracturing propping agent; Wherein, polyreaction water in mass ratio: dispersion agent: white clay: monomer: linking agent: carry out initiator=140:0.4~1.2:2~6:15~30:3.0~5.0:0.25~0.45.
2. utilize as claimed in claim 1 white clay to prepare the method for extremely-low density fracturing propping agents, it is characterized in that described coupling agent is silane coupling agent or aluminate coupling agent.
3. utilize as claimed in claim 1 white clay to prepare the method for extremely-low density fracturing propping agents, it is characterized in that described dispersion agent is Mg (OH) 2.
4. utilize as claimed in claim 1 white clay to prepare the method for extremely-low density fracturing propping agents, it is characterized in that described linking agent is divinylbenzene or cyclopentadiene.
5. utilize as claimed in claim 1 white clay to prepare the method for extremely-low density fracturing propping agents, it is characterized in that described initiator is benzoyl peroxide.
6. utilize as claimed in claim 1 white clay to prepare the method for extremely-low density fracturing propping agents, it is characterized in that adding dispersion agent at 60 ℃ of described polyreactions, after monomer solution drips, be warmed up to 75-80 ℃ of reaction 0.5-1h, 1-2h, 90-95 ℃ of reaction 1h of 85 ℃ of reactions finishes.
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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CN105623641A (en) * 2016-01-04 2016-06-01 钦州学院 Environment-friendly non-toxic support granules for shale gas extraction and preparation method thereof
CN105647503A (en) * 2016-01-04 2016-06-08 钦州学院 Nanoparticle static blasting agent for exploiting shale gas and preparation method of nanoparticle static blasting agent
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