CN101665686B - Method for preparing surface-modified proppant - Google Patents
Method for preparing surface-modified proppant Download PDFInfo
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- CN101665686B CN101665686B CN 200810146577 CN200810146577A CN101665686B CN 101665686 B CN101665686 B CN 101665686B CN 200810146577 CN200810146577 CN 200810146577 CN 200810146577 A CN200810146577 A CN 200810146577A CN 101665686 B CN101665686 B CN 101665686B
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 90
- 239000011347 resin Substances 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 42
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229920002521 macromolecule Polymers 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- 239000006004 Quartz sand Substances 0.000 claims description 41
- 239000004576 sand Substances 0.000 claims description 25
- -1 polysiloxane Polymers 0.000 claims description 21
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001165 hydrophobic group Chemical group 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 239000007849 furan resin Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 19
- 239000010410 layer Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 description 2
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940097156 peroxyl Drugs 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for preparing a surface-modified proppant, which comprises the following steps: (a) heating a proppant substrate to 100 to 240 DEG C; (b) adding resin into the heated matrix with stirring to form a mixture to allow the resin to be coated on the surface of the substrate and adding a macromolecular surfactant and a curing agent with stirring to cure the resin coated on the substrate; (c) adding lubricant and hydrophobic macromolecules before the caking of the mixture of the resin and the substrate; and (d) obtaining the proppant by cooling, crushing and screening the mixture obtained by the step c. The proppant prepared by the method has the advantage of stable environment corrosion resistance.
Description
Technical Field
The invention belongs to an oil and gas well propping agent in the field of oil field exploitation, and particularly relates to a preparation method of an oil and gas well propping agent in the field of oil field exploitation.
Background
Because the crude oil in the oil field has high viscosity, the rock stratum has low void ratio and poor void connectivity, great difficulty is brought to the oil extraction work. In order to increase the yield of crude oil and the rate of oil recovery, proppants are commonly used to increase formation voids and void connectivity. At first, quartz sand, ceramsite sand and the like are directly used as propping agents, but a large amount of fragments and fine silt are generated due to the fact that the propping agents need to bear large impact force and closing stress in the using process, and the fragments and the fine silt can block cracks so as to reduce the flow conductivity of the cracks. Therefore, at present, one or more resin films are generally coated on a substrate of a proppant such as quartz sand, ceramsite sand and the like to improve the fracture resistance of the proppant. However, due to the complicated downhole environment, the resin film on the surface of the proppant may be corroded by oil, oil gas, water, brine, steam, acid-base corrosive liquid, microorganisms and the like which are usually accompanied with the corrosion, degradation, falling off and the like of the coating layer, so that the flow conductivity of the fracture of the rock stratum is greatly reduced.
U.S. patent 2005244641 discloses a preparation method of a surface-modified oil and gas well hydraulic fracturing propping agent, namely a layer of hydrophobic substance is coated on the surface of a propping agent substrate, so that the environmental corrosion resistance of the propping agent is improved. The specific implementation mode is that sand grains are soaked in a hydrophobic substance, and after tens of minutes, the sand grains are taken out and dried. However, the prior art method still has the following defects: the purpose of modifying the surface resin layer of the propping agent is achieved by adopting a coating method, the hydrophobic polymer is attached to the resin layer, and due to the concentration difference between the inside and the outside of the resin layer, the hydrophobic polymer migrates to the inside of the resin layer through the permeation action and is wound in a resin network, so that the corrosion resistance of the resin layer is improved. On one hand, the hydrophobic macromolecules are only physically wound and fixed on the surface layer of the resin layer under weak acting force, and stronger acting force does not exist between the hydrophobic macromolecules and the resin layer to tightly combine the hydrophobic macromolecules and the resin layer; on the other hand, due to the fact that the potential energy of the surface of a substance is reduced, the potential energy of the surface of the hydrophobic macromolecule is low, the hydrophobic macromolecule is easy to migrate to the outer layer of the resin and is not easy to migrate to the inner part of the resin network, the acting force between the hydrophobic macromolecule and the resin layer is reduced, and therefore under the impact of the fracturing fluid, the hydrophobic layer is easy to fall off and the effect of improving the corrosion resistance of the proppant is lost; in addition, the hydrophobic substance is prepared into an aqueous solution, so that the concentration of the used spraying liquid or dipping liquid is not high, the content of the hydrophobic substance coated on the surface of the proppant is low, and the modification effect of the hydrophobic substance is not obvious.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is as follows: the method overcomes the defect that the corrosion resistance of the proppant is unstable due to the fact that a hydrophobic film on the surface of the proppant prepared by the method in the prior art is very easy to fall off, and provides the preparation method of the proppant with stable corrosion resistance.
In order to solve the technical problem, the invention provides a preparation method of a surface modified proppant, which comprises the following steps:
(a) heating the matrix of the proppant to 100-240 ℃;
(b) adding resin into the heated matrix and stirring to form a mixture so as to enable the resin to coat a film on the surface of the matrix, then adding a high molecular surfactant and a curing agent and stirring to enable the resin coated on the matrix to start curing, wherein the weight ratio of the resin to the matrix is 0.1-15:100, the addition amount of the curing agent is 5-30wt% of the weight of the resin, and the addition amount of the high molecular surfactant is 0.1-5wt% of the weight of the resin;
(c) adding a lubricant and a hydrophobic macromolecule into the resin-matrix mixture before the resin-matrix mixture starts to agglomerate, and stirring to form a mixture, wherein the adding amount of the lubricant is 0.1-10wt% of the weight of the resin, and the adding amount of the hydrophobic macromolecule is 0.1-10wt% of the weight of the resin;
(d) and c, cooling, crushing and screening the mixture obtained in the step c to obtain the proppant.
The hydrophobic polymer is one or more of polysiloxane, polysiloxane derivatives, polyolefin and halogenated polyolefin.
The addition amount of the high molecular surfactant is 0.2-1wt% of the weight of the resin. The hydrophobic units in the polymeric surfactant correspond to the hydrophobic groups in the hydrophobic polymer. For example, if the polymeric surfactant is polyether dimethyl siloxane, wherein the repeated hydrophobic units are dimethyl siloxane, and the hydrophobic groups of the hydrophobic polymer are dimethyl siloxane, the hydrophobic units in the polymeric surfactant correspond to the hydrophobic groups of the hydrophobic polymer.
The adding amount of the hydrophobic macromolecule is 0.2-2wt% of the weight of the resin.
In the step b, a step of adding a plasticizer is included before adding the curing agent, and the adding amount of the plasticizer is 1-30wt% of the weight of the resin.
The plasticizer is one or more of phthalate ester, aliphatic dibasic acid ester and phosphate ester, and the addition amount of the plasticizer is 10-20wt% of the weight of the resin.
The weight ratio of the resin to the matrix is 2-10: 100.
The addition amount of the curing agent is 10-20wt% of the weight of the resin, and the addition amount of the lubricant is 2-5wt% of the weight of the resin.
The resin is phenolic resin, and the corresponding curing agent is one or more of paraformaldehyde and hexamethylenetetramine; or the resin is furan resin, and the corresponding curing agent is one or more of benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid; or the resin is epoxy resin, and the corresponding curing agent is one or more of aliphatic amine and addition product thereof, tertiary amine and salt thereof, aromatic amine and modified product thereof, and imidazole; or the resin is unsaturated polyester resin, and the corresponding curing agent is one or more of peroxyacyl and peroxyester; or the resin is vinyl resin, and the corresponding curing agent is one or more of peroxyacyl and peroxyester.
The substrate is quartz sand and/or ceramsite sand, and the lubricant is one or more of polyethylene wax, oxidized polyethylene wax, stearic acid amide, ethylene bis-stearic acid amide, calcium stearate and zinc stearate.
In order to achieve the purpose of improving the environmental corrosion resistance, particularly the water corrosion resistance and the stability of the proppant, the invention introduces a high molecular surfactant into a resin layer coated on the surface of a substrate, and further adds a hydrophobic polymer in the resin curing process to improve the corrosion resistance, particularly the water corrosion resistance, of the whole proppant. The hydrophobic polymer is preferably one or more of siloxane, siloxane derivatives, polyolefin and halogenated polyolefin, and particularly preferably siloxane and siloxane derivatives, and mainly has low volatility, good lubricating property and wetting property. The specific mechanism of action is described next.
According to the invention, the macromolecular surfactant is added in the step b of preparing the proppant, on one hand, compared with the low molecular surfactant, the dispersibility and the thickening property of the macromolecular surfactant are better, so that the added curing agent, the added lubricant and the added hydrophobic macromolecule are more uniformly dispersed around the matrix coated with the resin film; on the other hand, due to the tendency of decreasing surface tension, the non-polar hydrophobic units on the long-chain polymer surfactant continuously migrate to the outer layer of the resin film during the resin curing process, so that the non-hydrophobic units are formed to be closely entangled with the cross-linked network generated during the resin curing process and the hydrophobic units are basically present on the surface layer of the resin film, in the subsequent step c, the hydrophobic groups in the hydrophobic polymers introduced during the resin curing process correspond to the hydrophobic units in the polymer surfactant, and because the same groups have strong affinity, strong electrostatic attraction is formed between the hydrophobic polymers and the hydrophobic units on the polymer surfactant on the surface layer of the resin layer, so that the hydrophobic polymers gradually migrate to the surface layer of the resin layer through the electrostatic attraction during the resin curing process, namely, a corrosion-resistant hydrophobic layer is formed on the surface of the resin layer, wherein the polymer surfactant plays a role in tightly connecting the hydrophobic polymer and the resin. The acting force is not easy to be damaged under acid-base environment and high-pressure impact to cause the degradation and falling of the resin layer, and the hydrophobic polymer basically positioned on the surface layer of the propping agent can be firmly combined with the resin, so that the corrosion resistance of the propping agent is improved, and the stability of the corrosion resistance is also improved. In general, a polymeric surfactant has a hydrophilic unit and a hydrophobic unit, and thus can function as a surfactant due to its structure.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the polymer surfactant and the hydrophobic polymer are introduced into the resin layer coated on the surface of the matrix in sequence, wherein the hydrophobic unit of the polymer surfactant corresponds to the hydrophobic group of the hydrophobic polymer, so that the interaction force between the hydrophobic polymer and the resin which are finally dispersed in the outer layer of the resin is greatly enhanced, and the stability of the environment erosion resistance of the surface-modified proppant in a rock stratum is improved.
(2) According to the invention, the surface modification substance of the propping agent, namely the hydrophobic polymer, is directly added in the resin curing process, so that on one hand, raw material loss caused in the process of solution preparation and the spray-dipping process of the traditional method can be avoided, the cost can be greatly saved, the introduction amount of the hydrophobic substance is not limited by the solution preparation concentration, and meanwhile, because water is not used as a solvent, the introduction of water molecules in the propping agent can be avoided, and the propping agent is further prevented from being corroded by the water molecules; on the other hand, hydrophobic macromolecules are introduced in the resin curing process, so that the winding degree between hydrophobic macromolecule chains and a formed resin network is higher, the acting force is stronger, and the hydrophobic macromolecule chains and the formed resin network are less prone to damage under the conditions of high pressure or acid-base and water vapor corrosion, namely, the stability of the environmental corrosion resistance, especially the water erosion resistance, is higher.
Detailed Description
Example 1
Heating 10kg of quartz sand of 20/40 meshes to 300 ℃, putting the quartz sand into a sand mixer, stirring the quartz sand, and cooling the quartz sand to 200 ℃. Adding 1kg of phenolic resin into the heated quartz sand, uniformly stirring to form a mixture, and then adding 0.01kg of polyether dimethyl siloxane and 0.2kg of hexamethylenetetramine, and uniformly stirring. When the phenolic resin-quartz sand mixture starts to agglomerate, 0.05kg of calcium stearate and 0.02kg of polydimethylsiloxane are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S1.
In this example, the purpose of heating is to provide a certain reaction temperature in the next step. In practical operation, the substrate may be heated to a higher temperature, such as 150-.
Hexamethylenetetramine is used as a curing agent to cure the resin on the surface of the quartz sand to form a resin layer with certain strength. The calcium stearate serves as a lubricant to enable the cured resin-matrix mixture to be more easily processed into particles and to ensure the integrity of the resin film and the smoothness of the surface, and to ensure that the proppant has excellent crush resistance during use.
Example 2
10kg of ceramsite sand is heated to 260 ℃ through an 20/40-mesh sieve, then placed into a sand mixer for stirring, and cooled to 100 ℃. 0.2kg of furan resin is added into the heated ceramsite sand and stirred uniformly to form a mixture, then 0.01kg of polyether methyl hydrogen siloxane and 0.04kg of dibutyl phthalate are added, and then 0.02kg of mixture of benzene sulfonic acid and toluene sulfonic acid is added and stirred uniformly. When the furan resin-ceramsite sand mixture begins to agglomerate, 0.004kg of ethylene bis stearamide and 0.02kg of polymethylhydrosiloxane are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S2.
Dibutyl phthalate acts as a plasticizer to improve the properties of the resin film, reduce its brittleness and increase its resistance to fracture.
Example 3
10kg of a mixture of quartz sand 20/40 meshes and ceramsite sand 20/40 meshes is heated to 300 ℃, then is put into a sand mixer to be stirred and is cooled to 240 ℃. Adding 1.5kg of furan resin into the heated mixture of the quartz sand and the ceramsite sand, uniformly stirring to form a mixed material, then adding 0.003kg of polyhydroxyvinylmethylhydrogensiloxane and 0.045kg of diisooctyl phthalate, and then adding 0.045kg of xylene sulfonic acid, and uniformly stirring. 0.15kg of a mixture of polyethylene wax and polyethylene oxide wax and 0.006kg of polymethylhydrosiloxane were added and stirred well before the mixture of furan resin-quartz sand and ceramsite sand began to agglomerate. The resulting mixture was cooled, crushed, and sieved to obtain proppant S3.
Example 4
10kg of quartz sand is heated to 260 ℃ through an 20/40-mesh sieve, then put into a sand mixer for stirring and cooled to 150 ℃. 0.01kg of epoxy resin is added into the heated quartz sand and stirred evenly to form a mixture, then 0.0002kg of polyvinyl chloride ether and 0.001kg of dibutyl adipate are added, and 0.002kg of aliphatic amine curing agent is added and stirred evenly. When the epoxy resin-quartz sand mixture begins to agglomerate, 0.001kg of stearic acid amide and 0.0004kg of polyvinyl chloride are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S4.
Example 5
Heating 10kg of quartz sand of 20/40 meshes to 300 ℃, putting the quartz sand into a sand mixer, stirring the quartz sand, and cooling the quartz sand to 200 ℃. 1kg of unsaturated polyester resin is added into the heated quartz sand and stirred uniformly to form a mixture, then 0.001kg of polyisobutylene ether and 0.01kg of diisooctyl sebacate are added, and 0.15kg of acyl peroxide curing agent is added and stirred uniformly. When the unsaturated polyester resin-quartz sand mixture begins to agglomerate, 0.001kg of zinc stearate and 0.002kg of polyisobutylene are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S5.
Example 6
10kg of ceramsite sand is heated to 300 ℃ through 20/40 meshes, then is put into a sand mixer to be stirred and is cooled to 200 ℃. Adding 0.5kg of vinyl resin into the heated ceramsite sand, uniformly stirring to form a mixture, then adding 0.0025kg of polyether methyl hydrogen siloxane, 0.075kg of triphenyl phosphate, and then adding 0.075kg of peroxyl curing agent, and uniformly stirring. When the vinyl resin-ceramsite sand mixture begins to agglomerate, 0.015kg of calcium stearate and 0.005kg of polymethylhydrosiloxane are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S6.
Example 7
Heating 10kg of quartz sand of 20/40 meshes to 300 ℃, putting the quartz sand into a sand mixer, stirring the quartz sand, and cooling the quartz sand to 200 ℃. 1kg of phenolic resin is added into the heated quartz sand and stirred uniformly to form a mixture, then 0.001kg of polyether siloxane, 0.25kg of tricresyl phosphate and triisooctyl phosphate are added, and 0.25kg of hexa-polyformaldehyde is added and stirred uniformly. When the phenolic resin-quartz sand mixture starts to agglomerate, 0.04kg of calcium stearate and 0.001kg of polydimethylsiloxane are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S7.
Example 8
Heating 10kg of quartz sand of 20/40 meshes to 300 ℃, putting the quartz sand into a sand mixer, stirring the quartz sand, and cooling the quartz sand to 200 ℃. 1kg of phenolic resin is added into the heated quartz sand and stirred evenly to form a mixture, then 0.003kg of polyether siloxane and 0.25kg of triisooctyl phosphate are added, and 0.25kg of hexamethylenetetramine is added and stirred evenly. 0.25kg of hexamethylenetetramine is stirred in a homogeneous manner. When the phenolic resin-quartz sand mixture starts to agglomerate, 0.07kg of calcium stearate and 0.01kg of polydimethylsiloxane are added and stirred uniformly. The resulting mixture was cooled, crushed, and sieved to obtain proppant S8.
Comparative example 1
Heating 10kg of quartz sand of 20/40 meshes to 300 ℃, putting the quartz sand into a sand mixer, stirring the quartz sand, and cooling the quartz sand to 200 ℃. Adding 1kg of phenolic resin into the heated quartz sand, uniformly stirring to form a mixture, and then adding 0.2kg of hexamethylenetetramine, and uniformly stirring. When the phenolic resin-quartz sand mixture starts to agglomerate, 0.05kg of calcium stearate is added and stirred uniformly. And cooling, crushing and sieving the obtained mixture to obtain the front proppant of the proppant before the proppant is not coated with the hydrophobic polymer.
The front support agent is soaked in polydimethylsiloxane aqueous solution with the concentration of 5wt%, and after soaking for 2 hours, the front support agent is dried at normal temperature to obtain the support agent C1.
Evaluation examples
The samples from examples 1 to 8 and comparative example 1 were tested for acid solubility, turbidity and proppant conductivity using the samples from S1 to S8 and C1. Wherein,
the acid solubility refers to the percentage of the mass of the proppant dissolved by the acid to the original mass of the proppant in a specified acid solution and acid dissolution time, and the specific operating conditions are as follows: each proppant was immersed in a 0.5mol/L phosphoric acid solution for 1 hour, washed and dried, and then each weight was measured to calculate the weight dissolved, and the acid solubility was measured by the method described above.
Turbidity is measured by adding a certain amount of support into a specified volume of distilled water, heating at 50 deg.C for 60 min, and stirring for a while.
The test condition of the flow conductivity of the proppant is that in an API standard flow guide chamber, an equal mass measurement method is adopted, and the sand laying concentration is 5.0kg/m2The test fluid was a 2wt% KCl solution and the closure pressure was 20 MPa.
The results of the above tests are shown in Table 1.
TABLE 1
| Proppant samples | Acid solubility wt ‰ | Turbidity NTU | Conductivity mum2·cm |
| S1 | 0.1 | 4 | 157.4 |
| S2 | 0.2 | 3 | 154.9 |
| S3 | 0.3 | 6 | 144.6 |
| S4 | 0.7 | 10 | 139.2 |
| S5 | 0.5 | 7 | 137.0 |
| S6 | 0.4 | 7 | 142.7 |
| S7 | 0.3 | 5 | 145.3 |
| S8 | 0.2 | 4 | 152.8 |
| C1 | 4.7 | 56 | 117.3 |
As can be seen from the data in Table 1, compared with the proppant C1 prepared by adopting the traditional method of introducing hydrophobic macromolecules and not adding high molecular surfactants by a spray-dip coating method, the acid corrosion resistance of each proppant of introducing the high molecular surfactants and the hydrophobic macromolecules in the resin curing process is obviously improved, the substances dissolved in water are obviously reduced, and the modified proppant has excellent flow conductivity under higher closing pressure, so that the hydrophobic macromolecules enriched in the outer layer of the proppant have the function of improving the corrosion resistance of the proppant to substances such as water, acid and the like after the proppant is modified, and compared with the traditional preparation method of not adding the high molecular surfactants and adopting the spray-dip method for modification, the modification effect of the invention is more obvious, the environment corrosion resistance of the proppant is more stable, and the introduced hydrophobic macromolecules are enriched in the surface layer of the proppant and have stronger resistance to resin films on the substrate The acting force has stable erosion resistance in the environment, and the defect that the flow conductivity of a rock stratum gap is reduced due to the fact that the propping agent is eroded and a resin layer falls off to cause the breaking of the propping agent can be avoided in practical application, and the service life of the propping agent is correspondingly prolonged.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to fall within the scope of the appended claims.
Claims (9)
1. A method of preparing a surface modified proppant comprising the steps of:
(a) heating the matrix of the proppant to 100-240 ℃;
(b) adding resin into the heated matrix and stirring to form a mixture so as to enable the resin to coat a film on the surface of the matrix, then adding a high molecular surfactant and a curing agent and stirring to enable the resin coated on the matrix to start curing, wherein the weight ratio of the resin to the matrix is 0.1-15:100, the addition amount of the curing agent is 5-30wt% of the weight of the resin, and the addition amount of the high molecular surfactant is 0.1-5wt% of the weight of the resin;
(c) adding a lubricant and a hydrophobic macromolecule into the resin-matrix mixture before the resin-matrix mixture starts to agglomerate, and stirring to form a mixture, wherein the adding amount of the lubricant is 0.1-10wt% of the weight of the resin, and the adding amount of the hydrophobic macromolecule is 0.1-10wt% of the weight of the resin;
(d) cooling, crushing and screening the mixture obtained in the step c to obtain the proppant;
the resin is phenolic resin, and the corresponding curing agent is one or more of paraformaldehyde and hexamethylenetetramine; or
The resin is furan resin, and the corresponding curing agent is one or more of benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid; or
The resin is epoxy resin, and the corresponding curing agent is one or more of aliphatic amine and addition product thereof, tertiary amine and salt thereof, aromatic amine and modified product thereof, and imidazole; or
The resin is unsaturated polyester resin, and the corresponding curing agent is one or more of peroxyacyl and peroxyester; or
The resin is vinyl resin, and the corresponding curing agent is one or more of peroxyacyl and peroxyester.
2. The method of making a surface modified proppant of claim 1, wherein: the hydrophobic polymer is one or more of polysiloxane, polysiloxane derivatives, polyolefin and halogenated polyolefin.
3. A method of making a surface modified proppant as set forth in claim 1 or 2, characterized in that: the addition amount of the high molecular surfactant is 0.2-1wt% of the weight of the resin, and the hydrophobic units in the high molecular surfactant correspond to the hydrophobic groups in the hydrophobic high polymer.
4. A method of making a surface modified proppant as set forth in claim 1 or 2, characterized in that: the adding amount of the hydrophobic macromolecule is 0.2-2wt% of the weight of the resin.
5. The method of making a surface modified proppant of claim 1, wherein: in the step b, a step of adding a plasticizer is included before adding the curing agent, and the adding amount of the plasticizer is 1-30wt% of the weight of the resin.
6. The method of making a surface modified proppant of claim 5, wherein: the plasticizer is one or more of phthalate ester, aliphatic dibasic acid ester and phosphate ester, and the addition amount of the plasticizer is 10-20wt% of the weight of the resin.
7. The method of making a surface modified proppant of claim 1, wherein: the weight ratio of the resin to the matrix is 2-10: 100.
8. The method of making a surface modified proppant of claim 1, wherein: the addition amount of the curing agent is 10-20wt% of the weight of the resin, and the addition amount of the lubricant is 2-5wt% of the weight of the resin.
9. The method of making a surface modified proppant of claim 1, wherein: the substrate is quartz sand and/or ceramsite sand, and the lubricant is one or more of polyethylene wax, oxidized polyethylene wax, stearic acid amide, ethylene bis-stearic acid amide, calcium stearate and zinc stearate.
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| CN108751915B (en) * | 2018-06-28 | 2022-02-01 | 中国石油天然气股份有限公司 | Water plugging fracturing tectorial membrane proppant for bottom water reservoir and preparation method |
| CN109337669A (en) * | 2018-11-27 | 2019-02-15 | 江苏华普泰克石油装备有限公司 | A kind of high-strength low-density petroleum propping agent and preparation method thereof |
| CN110452495A (en) * | 2019-08-26 | 2019-11-15 | 衡水建胜橡塑科技有限公司 | A kind of high molecular polymer modifying agent |
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