CN1329420C - Cladded quartz sand fracturing support agent for oil production - Google Patents

Cladded quartz sand fracturing support agent for oil production Download PDF

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CN1329420C
CN1329420C CNB2004100010029A CN200410001002A CN1329420C CN 1329420 C CN1329420 C CN 1329420C CN B2004100010029 A CNB2004100010029 A CN B2004100010029A CN 200410001002 A CN200410001002 A CN 200410001002A CN 1329420 C CN1329420 C CN 1329420C
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resin
quartz sand
weight ratio
agent
oil recovery
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CN1640981A (en
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秦升益
张伟民
仁国平
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Beijing Rechsand Science and Technology Group Co Ltd
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BEIJING RENCHUANG MANUFACTURE TECHNOLOGY RESEARCH INSTITUTE
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Abstract

The present invention relates to a fracturing propping agent for oil production and a manufacturing method thereof. The propping agent comprises quartz sand granules and hardened thermosetting resin films coated on the surfaces of the quartz sand granules. The propping agent of the present invention has the advantages of high crushing resistance and low cost, and the present invention can be used for replacing hadite sand with high price.

Description

The film coverd quartz sand fracturing propping agent for oil recovery
Technical field
The present invention relates to a kind of The film coverd quartz sand fracturing propping agent for oil recovery and its manufacture method.
Background technology
The crude oil viscosity is big, and the rock stratum voidage is low, and the space is connective poor, has brought very big difficulty to oil extraction operation.In order to improve oil recovery factor and oil recovery rate, reduce cost, generally adopt fracturing propping agents to improve rock stratum voidage and space connectedness at present, obtained good effect.Propping agent commonly used is quartz sand and haydite sand.Quartz sand is inexpensive, and about 200 yuan per ton, but intensity is not high, anti-percentage of damage is low, and under the closure stress condition with higher, sand grains will be crushed, produce a large amount of fragment and fine silt, these fine silts move in the crack and stop up the crack, thereby reduce fissured flow conductivity; The anti-breaking capacity height of haydite sand, but owing to cost an arm and a leg, about 1600 yuan per ton, high-strength ceramsite sand price is more expensive, and price is about 2200 yuan, simultaneously because the relative density of haydite sand is big, in construction, require the viscosity height of sand-carrying agent, energy charge is big, and the whole construction expense is also quite high, is only limited in the high stratum of locking pressure and uses.
The content of invention
Purpose of the present invention is exactly the problems referred to above that overcome prior art, and a kind of novel oil recovery fracturing propping agents are provided, and increases anti-breaking capacity, reduces the propping agent cost, improves the productive rate of crude oil.
Oil recovery of the present invention comprises quartz sand particle with fracturing propping agents and is coated on the resin molding of quartz sand particle surface cure.
The solidified resin molding of propping agent of the present invention has the inner netted three dimensional structure that is, and is softening at the Shi Buhui that is heated, thereby has intensity, in addition, because resin molding has certain toughness, thereby in use can reduce percentage of damage greatly, can substitute expensive haydite sand propping agent.
On the basis of the above, the present invention recovers the oil and with the further modification of fracturing propping agents is:
1, forming the resin of described resin molding and the weight ratio of quartz sand is 0.1-15: 100.
2, the weight ratio of described resin and quartz sand is preferably 2-10: 100.
3, described quartz sand is common quartz sand, washing quartz sand or the pickling quartz sand of particle diameter 0.225-1.25mm.The particle diameter of quartz sand can be selected according to actual needs, and the purpose of use washed-out sand or pickling sand is to remove the impurity or the micro mist of sand grain surface, improves the cohesive strength of resin and sand grains.
4, contain softening agent in the described resin molding, the weight ratio of softening agent and resin is 1-30: 100.The purpose that adds softening agent is to improve the resin molding performance, reduces its fragility, increases anti-breaking capacity.
The present invention makes the method for recovering the oil with fracturing propping agents and comprises the following steps:
(1) quartz sand is heated to 100-240 ℃;
(2) in the quartz sand of heating, add resin earlier, and stir, make resin at the quartz sand particle surface coating, and then add solidifying agent and stir, make the resin that is coated on the quartz sand particle surface begin to solidify, the weight ratio of resin and quartz sand is 0.1-15: 100;
(3) at quartz sand--resin mixture the adding lubricant occurs before the agglomerating phenomenon of caking and stirs;
(4) cooling, broken, sieve above-mentioned quartz sand--resin compound, obtain the finished product.
Based on the above method, the present invention has following modification:
1, comprises also in the described step (1) that elder generation is heated to 150-300 ℃ with quartz sand, makes its temperature reduce to 100-240 ℃ step then.Elder generation's heat is cooled to 100-240 ℃ purpose again and is to make the quartz sand temperature when adding resin even, can also remove the volatile matter (as organism) of sand grain surface simultaneously, thereby increases the cohesive strength of resin and sand grains.
2, before the step of described adding solidifying agent, also comprise the step that adds softening agent and stir.The purpose that adds softening agent is to improve the resin molding performance, reduces its fragility, increases anti-breaking capacity.At this, term " before the step of described adding solidifying agent " both is meant also can be after resin adds before resin adds, can also be to add simultaneously with resin.
3, described softening agent is adjacent benzene type dicarboxylic acid esters, aliphatics dicarboxylic acid esters, phosphoric acid ester or their mixture, and the weight ratio of itself and resin is 1-30: 100.
4, the weight ratio of described softening agent and resin is preferably 10-20: 100.
5, also comprised the step that adds silane coupling agent and stir before the step of described adding solidifying agent or resin, the weight ratio of itself and resin is 0.1-10: 100.The purpose that adds silane coupling agent also is the cohesive strength that strengthens resin and sand grains, improves its anti-breaking capacity.At this, term " before the step of described adding solidifying agent " both is meant also can be after resin adds before resin adds, can also be to add simultaneously with resin.
6, the weight ratio of described coupling agent and resin is preferably 0.5-5: 100.The silane coupling agent add-on is too high, and is little to the increase influence of cohesive strength, and can increase cost.
7, described lubricant is polyethylene wax, oxidized polyethlene wax, stearic amide, ethylene bis stearic acid amide, calcium stearate or Zinic stearas, and the weight ratio of itself and resin is 0.1-10: 100.The purpose that adds lubricant be to make after the curing sand--resin compound is broken easily, guarantee the integrity of resin molding, improve its anti-breaking capacity.
8, the weight ratio of described lubricant and resin is preferably 2-5: 100.
9, described thermosetting resin is (1) resol, (2) Resins, epoxy, (3) unsaturated polyester resin or (4) Vinylite, their pairing solidifying agent are respectively (1) Paraformaldehyde 96 or hexamethylenetetramine, (2) fatty amine and affixture, tertiary amine and salt thereof, aromatic amine and modification body thereof, imidazoles, polymer performed polymer, (3) acyl peroxide class, peroxyester, (4) acyl peroxide class, peroxyester, and the weight ratio of solidifying agent and resin is 0.5-30: 100.
Above-mentioned resin used in the present invention can be independent, also can mix use.Resol optional heat solidity or novolac resin.The solidifying agent of novolac resin is Paraformaldehyde 96 or hexamethylenetetramine; In order to make the heat-reactive phenolic resin completion of cure, add a small amount of hexamethylenetetramine.Optional liquid state of Resins, epoxy or solid epoxy resin, the softening temperature of solid epoxy resin preferably are not higher than 140 ℃, and too high softening temperature influences the homogeneity of overlay film, and be unfavorable to the anti-breaking capacity that strengthens propping agent; Curing agent for epoxy resin is of a great variety, and solidifying agent can be selected fatty amine, cycloaliphatic amines and affixture thereof, tertiary amine and salt thereof, aromatic amine and modification body thereof, imidazoles and some polymer performed polymers (polymeric amide, aminoresin, amino urethane).Unsaturated polyester resin can be selected 3301 unsaturated polyester resins of erosion resistance, 197 unsaturated polyester resins and dimethylbenzene unsaturated polyester resin, and solidifying agent is selected acyl peroxide class (benzoyl peroxide, lauroyl peroxide), peroxyester.The solidifying agent that Vinylite uses is identical with unsaturated polyester resin.
Softening agent of the present invention is adjacent benzene type dicarboxylic acid esters (as dibutyl phthalate, dimixo-octyl phthalate), fatty group dibasic acid (as Polycizer W 260, di-isooctyladinpate, Uniflex DBS, diisooctyl sebacate) and phosphoric acid ester (triphenylphosphate, tricresyl phosphate (β-chloroethene ester), Tritolyl Phosphate, diphenyl octyl phosphate, triisooctyl phosphate), these a few class softening agent can use or mix use separately, consumption accounts for the 1-30% of resin, preferably 10-20%.
Coupling agent can be silane coupling agent, as amine propyl-triethoxysilicane, glycidoxy-propyltrimethoxy silane, anilinomethyl triethoxysilane etc.
Embodiment
Embodiment 1
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs, the resol that adds 3g when cooling to 200 ℃ stirs, add the solidifying agent hexamethylenetetramine then, resin molding is solidified, begin to solidify and conglomeration (piece) preceding adding lubricant stearic acid calcium and stirring at resin, preferably cooling, broken, sieve, obtain the finished product proppant in high intensity.
The add-on of calcium stearate and the weight ratio of resin are respectively 0.1: 100,0.5: 100,1: 100,5: 100,10: 100.
Embodiment 2
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs, the resol that adds 30g when cooling to 200 ℃ stirs, add the solidifying agent hexamethylenetetramine then, resin molding is solidified, begin to solidify and beginning conglomeration (piece) preceding adding lubricant stearic acid calcium and stirring at resin, preferably cooling, broken, sieve, obtain the finished product proppant in high intensity.
Embodiment 3
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs, the resol that adds 120g when cooling to 200 ℃ stirs, add the solidifying agent hexamethylenetetramine then, resin molding is solidified, begin to solidify and beginning conglomeration (piece) preceding adding lubricant stearic acid calcium and stirring at resin, preferably cooling, broken, sieve, obtain the finished product proppant in high intensity.
Embodiment 4
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs, the resol that adds 300g when cooling to 200 ℃ stirs, add the solidifying agent hexamethylenetetramine then, resin molding is solidified, begin to solidify and beginning conglomeration (piece) preceding adding lubricant stearic acid calcium and stirring at resin, preferably cooling, broken, sieve, obtain the finished product proppant in high intensity.
Embodiment 5
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs, the resol that adds 450g when cooling to 200 ℃ stirs, add the solidifying agent hexamethylenetetramine then, resin molding is solidified, begin to solidify and beginning conglomeration (piece) preceding adding lubricant stearic acid calcium and stirring at resin, preferably cooling, broken, sieve, obtain the finished product proppant in high intensity.
Embodiment 6
In the foregoing description 1-5, before adding solidifying agent, add the adjacent benzene type of softening agent dicarboxylic acid esters, aliphatics dicarboxylic acid esters, phosphoric acid ester or their mixture respectively, and stir, the weight ratio of itself and resin is 1: 100,5: 100,10: 100,20: 100,30: 100.Other is identical.
Embodiment 7
In the foregoing description 1-6, before adding solidifying agent or adding resin, add silane coupling agent amine propyl-triethoxysilicane, glycidoxy-propyltrimethoxy silane, anilinomethyl triethoxysilane respectively, and stir, the weight ratio of itself and resin is 0.1: 100,0.5: 100,1: 100,5: 100,10: 100.
Embodiment 8
In the foregoing description 1-7, with lubricator polyethylene wax, oxidized polyethlene wax, stearic amide, ethylene bis stearic acid amide, Zinic stearas replace lubricant stearic acid calcium, and other is constant.
Embodiment 9
In the foregoing description 1-8, replace resol with (1) Resins, epoxy, (2) unsaturated polyester resin or (3) Vinylite, their pairing solidifying agent are respectively (1) fatty amine and affixture, tertiary amine and salt thereof, aromatic amine and modification body thereof, imidazoles, polymer performed polymer, (2) acyl peroxide class, peroxyester, (3) acyl peroxide class, peroxyester, and other is identical.
Example 10
Putting into sand mill after 3kg quartz sand 20/40 order is heated to 260 ℃ stirs; The resol that adds 120g when cooling to 200 ℃ stirs; The mixture and the solidifying agent hexamethylenetetramine 18g of the adjacent benzene type dicarboxylic acid esters of adding 12g and the amine propyl-triethoxysilicane of 1.2g, the calcium stearate that adds 8g subsequently stirs; Cooling, broken, sieve, obtain the finished product proppant in high intensity.
Example 11
Add the resol of 90g, the Resins, epoxy of 30g, other identical embodiment 10.
Example 12
The Resins, epoxy, the solidifying agent that add 120g are aromatic amine 24g, other identical embodiment 10.
Example 13
The resol that adds 60g, Resins, epoxy 30g, hexamethylenetetramine 9g, aryl tertiary amine 3g, other identical embodiment 10.
Be the comparison that propping agent of the present invention and common quartz sand are made propping agent below.
Table 1 quartz sand compares with the quartz sand propping agent percentage of damage of overlay film
Propping agent Specification (particle diameter) (mm) Volume density (g/cm 3) Volume density (g/cm 3) Turbidity (NTU) Acid solubility (%) Percentage of damage (%)
28 MPa 52 MPa 69 MPa 86 MPa
Quartz sand 0.45-0.9 1.64 2.64 128 4.64 6.71 25.59 36.14
Example 11 0.45-0.9 1.58 2.31 5 0.03 0.27 1.19 2.52 3.60
Example 13 0.45-0.9 1.58 2.47 31 0.12 0.30 2.00 3.76 5.01
The different locking pressure lower support of table 2 agent short-term flow conductivity relatively
Figure C20041000100200101
Annotate: API diversion chamber, wait mass method; Sanding concentration 5.0Kg/m 2, Experimental Flowing Object is 2% KCl liquid
The implication of each term is in the table:
" acid solubility " is meant at the acid solution of regulation and in the sour molten time, determines that the certain mass propping agent is by the per-cent of sour dissolved quality with total propping agent quality.
" turbidity " is meant the propping agent that adds certain volume in the distilled water of prescribed volume, stirs the muddy degree of liquid then.
" volume density " is meant the propping agent of unit mass and the ratio of its particle volume.
" volume density " is meant the propping agent of unit mass and the ratio of its stacking volume.
" anti-breaking capacity " is meant the propping agent to certain volume, carries out the pressure-bearing test under fixation pressure.
As can be seen, propping agent of the present invention is compared with common quartz sand propping agent from table 1, table 2, but its breaking capacity and flow conductivity all are improved largely.
Above-mentioned just illustrative to the description of invention with reference to embodiment, and do not constitute qualification to it.Obviously, can carry out many modification or improvement to the present invention on the basis of the above, but all can the not break away from the present invention essence of " coating the solidified resin molding on quartz sand particle surface, to strengthen the anti-breaking capacity of propping agent ".

Claims (13)

1, a kind of oil recovery fracturing propping agents is characterized in that, this propping agent comprises quartz sand particle and be coated on the resin molding of quartz sand particle surface cure, and described resin molding comprises resin and softening agent, and the weight ratio of described softening agent and resin is 1-30: 100.
2, oil recovery fracturing propping agents according to claim 1 is characterized in that, forming the resin of described resin molding and the weight ratio of quartz sand is 0.1-15: 100.
3, oil recovery fracturing propping agents according to claim 2 is characterized in that, the weight ratio of described resin and quartz sand is 2-10: 100.
According to the described oil recovery fracturing propping agents of one of claim 1-3, it is characterized in that 4, described quartz sand is washing quartz sand or the pickling quartz sand of particle diameter 0.225-1.25mm.
5, a kind of method of making the described oil recovery of claim 2 with fracturing propping agents is characterized in that this method comprises the following steps:
(1) quartz sand is heated to 100-240 ℃;
(2) add resin in the quartz sand with heating earlier, and stir, make resin at the quartz sand particle surface coating, the adding softening agent also stirs, and then add solidifying agent and stir, make the resin that is coated on the quartz sand particle surface begin to solidify, the weight ratio of resin and quartz sand is 0.1-15: 100;
(3) at quartz sand--resin mixture the adding lubricant occurs before the agglomerating phenomenon of caking and stirs;
(4) cooling, broken, sieve above-mentioned quartz sand-resin compound, obtain the finished product.
6, method according to claim 5 is characterized in that, also comprises in the described step (1) earlier quartz sand being heated to 150-300 ℃, makes its temperature reduce to 100-240 ℃ step then.
7, method according to claim 5 is characterized in that, described softening agent is adjacent benzene type dicarboxylic acid esters, aliphatics dicarboxylic acid esters, phosphoric acid ester or their mixture, and the weight ratio of itself and resin is 1-30: 100.
8, method according to claim 7 is characterized in that, the weight ratio of described softening agent and resin is 10-20: 100.
9, according to the described method of one of claim 5-8, it is characterized in that, also comprised the step that adds silane coupling agent and stir before the step of described adding solidifying agent or resin, the weight ratio of itself and resin is 0.1-10: 100.
10, method according to claim 9 is characterized in that, the weight ratio of described coupling agent and resin is 0.5-5: 100.
11, according to the described method of one of claim 5-8, it is characterized in that described lubricant is that the weight ratio of polyethylene wax, oxidized polyethlene wax, stearic amide, ethylene bis stearic acid amide, calcium stearate or Zinic stearas, itself and resin is 0.1-10: 100.
12, method according to claim 11 is characterized in that, the weight ratio of described lubricant and resin is 2-5: 100.
13, according to the described method of one of claim 5-8, it is characterized in that, described resin is (1) resol, (2) Resins, epoxy, (3) unsaturated polyester resin or (4) Vinylite, their pairing solidifying agent are respectively (1) Paraformaldehyde 96 or hexamethylenetetramine, (2) fatty amine and affixture, tertiary amine and salt thereof, aromatic amine and modification body thereof, imidazoles, polymer performed polymer, (3) acyl peroxide class, peroxyester, (4) acyl peroxide class, peroxyester, and the weight ratio of solidifying agent and resin is 0.5-30: 100.
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