CN106190094B - Environment-friendly high-strength resin coated proppant - Google Patents
Environment-friendly high-strength resin coated proppant Download PDFInfo
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- CN106190094B CN106190094B CN201610560919.5A CN201610560919A CN106190094B CN 106190094 B CN106190094 B CN 106190094B CN 201610560919 A CN201610560919 A CN 201610560919A CN 106190094 B CN106190094 B CN 106190094B
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- 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
Abstract
The invention relates to an environment-friendly high-strength resin coated proppant, which comprises aggregate, environment-friendly resin, a catalyst, a dispersing agent, a drying agent and an anti-blocking agent, wherein the environment-friendly resin comprises a substance containing terminal hydroxyl and a substance containing isocyanate groups. On the basis of keeping the effect of the traditional propping agent, the environment and the human body can be better protected, the energy is saved, the cost is saved, and meanwhile, the proppant also has the advantages of high strength and low breakage.
Description
Technical Field
The invention belongs to the technical field of oil and gas field exploitation, belongs to a composition for reinforcing a fracture action, such as a proppant composition for keeping the fracture open, and particularly relates to an environment-friendly high-strength resin coated proppant.
Background
Conventional and unconventional oil and gas production technologies have developed relatively mature in north american countries and today's production technologies in china have made great progress. The tectorial membrane proppant is widely applied to hydraulic fracturing construction, but because a large amount of fracturing fluid is used in the hydraulic fracturing construction process, a large amount of fracturing fluid is discharged back to the ground in the construction process, and the pollution of surface water can be caused.
At present, the materials used by the tectorial membrane proppant in China are basically phenolic aldehyde and epoxy resin, and the resins can generate toxic and harmful substances such as free phenol, free aldehyde and the like in the production and application processes. The curing of phenolic aldehyde and epoxy resin needs to add various curing agents, wherein the most common curing agent is urotropine which generates a large amount of ammonia gas at high temperature and causes harm to the environment and workers. The returned fracturing fluid of many fracturing constructions can seriously pollute the environment for the reasons. And the traditional tectorial membrane proppant in China is broken under the condition of tectorial membrane with low resin content, and a plurality of indexes such as acid solubility and the like can not meet the requirements. Based on the background, it is necessary to develop a coated proppant product with environmental protection characteristics.
Disclosure of Invention
The invention aims to provide an environment-friendly high-strength resin coated propping agent which has the characteristics of safe and environment-friendly production and use and reduces the pollution to the environment.
In order to achieve the purpose, the technical scheme of the invention is as follows: the environment-friendly high-strength resin coated proppant comprises aggregate, environment-friendly resin, a catalyst, a dispersing agent, a drying agent and an anti-blocking agent, wherein the environment-friendly resin comprises a substance containing terminal hydroxyl groups and a substance containing isocyanate groups.
When the technical scheme is adopted, on the basis of keeping the effect of the traditional propping agent, the environment and the human body can be better protected, the energy is saved, the cost is saved, and meanwhile, the proppant also has the advantages of high strength and low breakage. Compared with the traditional resin coated propping agent, the proppant also has the following advantages:
environmental protection property: the traditional resin film-coated propping agent uses phenolic aldehyde, epoxy resin film can generate toxic and harmful substances such as free phenol, free aldehyde, ammonia gas and the like in the high-temperature production process, and the environment-friendly resin can be safely and environmentally produced under the condition of low-temperature film coating.
Product properties at the same resin amount: the invention has better index performance such as density, apparent density, breaking and the like under the condition of the same amount of resin coating.
Energy conservation: the film coating temperature of the traditional resin film coating propping agent is 230 ℃, and the film coating temperature of the invention is 60-150 ℃. The present invention is very advantageous in view of energy consumption.
Change of the appearance of the aggregate: the traditional resin coated proppant is easy to change the color and the grain size of aggregate by coating the film with high-temperature resin.
The effect of low resin content is obvious: under the condition that the resin amount is less than 1%, the traditional resin coated propping agent does not change the crushing of the aggregate greatly, and the invention can effectively improve the crushing condition of the aggregate under the condition of low resin amount.
In a further improvement, the substance containing terminal hydroxyl groups comprises one or a mixture of two or more of polyols, polyethers, aromatic alcohols, polyesters and castor oil modified polyols.
In a further improvement, the substance containing isocyanate groups comprises one of diphenylmethane diisocyanate, isophorone diisocyanate, polyphenyl polymethylene polyisocyanate, toluene diisohydrocarbonate, hexamethylene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, tetramethyl m-phenylene diisocyanate or a mixture of two or more of them.
In a further improvement, the weight ratio of the substance containing terminal hydroxyl groups to the substance containing isocyanate groups is 0.3-5.
In a further improvement scheme, the aggregate comprises one or a mixture of two or more of ceramsite, low-density ceramsite, ceramic material, quartz sand particles, walnut shells, resin material, rubber material and glass material.
In a further improvement scheme, the weight of the environment-friendly resin is 0.25-5% of the weight of the aggregate.
In a further improvement, the catalyst comprises one of organic acid lead, organic tin and polyether or a mixture of two or more of the organic acid lead, the organic tin and the polyether.
In a further improvement, the anti-caking agent comprises one or a mixture of two or more of calcium stearate, stearic acid amide, zinc stearate, magnesium stearate, paraffin, synthetic paraffin, carnauba wax, alkylamide, polyamide, cellulose and calcium carbonate.
Detailed Description
The following examples are provided to better understand the present invention and are not to be construed as being limited to the preferred embodiments described herein.
The aggregate selected by the invention is quartz sand particles or a mixture of ceramsite and quartz sand particles. The particle size of the granules was 1180/850 μm (16/20 mesh), 1180/600 μm (16/30 mesh), 850/425 μm (20/40 mesh), 600/300 μm (30/50 mesh), 300/150 μm (50/100 mesh), 425/212 μm (40/70 mesh) or 212/109 μm (70/140 mesh). The particle size distribution meets the industrial standard SY/T5108-2014. The examples of the present invention are carried out according to conventional techniques or conditions described in the literature in the art, unless otherwise specified. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be purchased in the market.
The environment-friendly resin A in the following embodiments is a substance containing a terminal hydroxyl group, and includes one or a mixture of two or more of polyols, polyethers, aromatic alcohols, polyesters, castor oil-modified polyols. The environment-friendly resin B is a substance containing isocyanate groups and comprises one or a mixture of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, polyphenyl polymethylene polyisocyanate, toluene diisocynate, hexamethylene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and tetramethyl m-phenylene diisocyanate.
Example 1
Heating 2 kg of quartz sand particles with the particle size of 1180/600 mu m (16/30 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to about 85 ℃, adding 13.8 g of environment-friendly resin A, stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate), stirring for 35 seconds, adding 6.2 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling, and sieving to obtain the environment-friendly resin coated proppant.
Example 2
Heating 2 kg of quartz sand particles with the particle size of 850/425 mu m (20/40 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 13.8 g of environment-friendly resin A, stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate), and stirring for 35 seconds; adding 6.2 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 3
Heating 2 kg of quartz sand particles with the particle size of 600/300 mu m (30/50 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 13.8 g of environment-friendly resin A, stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate), and stirring for 35 seconds; adding 6.2 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 4
Heating 2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 13.8 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 6.2 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 5
Heating 2 kg of quartz sand particles with the particle size of 212/106 mu m (70/140 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 13.8 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 6.2 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
| Experiment number | Grain size of sand | Amount of resin (%) | Body weight density (g/ml3) | Optic secret (g/ml3) | Crushing (%) | Acid soluble (%) |
| Example 1 | 16/30 | 1.00 | 1.56 | 2.60 | 0.40 | 2.57 |
| Example 2 | 20/40 | 1.00 | 1.58 | 2.56 | 0.49 | 3.51 |
| Example 3 | 30/50 | 1.00 | 1.52 | 2.60 | 1.01 | 2.76 |
| Example 4 | 40/70 | 1.00 | 1.55 | 2.58 | 0.56 | 3.50 |
| Example 5 | 70/140 | 1.00 | 1.33 | 2.61 | 2.13 | 2.21 |
Remarking: the crushing requirements are measured according to SY/T5108-2014, wherein 16/30 crushing requirements are 14MPa, 20/40 crushing requirements are 28MPa, and other crushing requirements are 35 MPa.
The quartz sand particles with different particle sizes are used as the aggregate, when the resin amount accounts for 1% of the weight of the aggregate, the prepared environment-friendly resin coated proppant has density, acid solubility and breakage, can reach the standard of SY/T5108-2014 in the industry, and is better than the traditional resin coated proppant under the condition of the same resin amount.
Example 6
Heating 2 kg of quartz sand particles with the particle size of 212/106 mu m (70/140 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 11 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 5 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 7
Heating 2 kg of quartz sand particles with the particle size of 212/106 mu m (70/140 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 8
Heating 2 kg of quartz sand particles with the particle size of 212/106 mu m (70/140 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 4.13 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 1.87 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the product.
Under the condition of adding low-amount resin coating, the 70/140-mesh quartz sand particles can obtain better crushing effect under the condition of the traditional coating with the same resin amount, wherein the experimental effect is best when the resin amount is 1 percent.
Example 9
Heating 2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 45 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 10
Heating 2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 65 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 11
Heating 2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 85 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 12
Heating 2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) to 120 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 105 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
Example 13
Heating 2 kg of quartz sand particles with the particle size of 425/212 μm (40/70 meshes) to 150 ℃, putting the quartz sand particles into a sand mixer for stirring, cooling to 125 ℃, adding 6.9 g of environment-friendly resin A for stirring for 20 seconds, adding 0.1 g of organic acid lead (such as lead isooctanoate) for stirring to 35 seconds; adding 3.1 g of environment-friendly resin B, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 80 seconds, cooling and sieving to obtain the environment-friendly resin coated proppant.
| Experiment number | Grain size of sand | Coating temperature (. degree.C.) | Body weight density (g/ml3) | Optic secret (g/ml3) | Acid soluble (%) | Crushing (48mpa) |
| Example 9 | 40/70 | 45 | 1.51 | 2.59 | 4.76 | 11.5 |
| Example 10 | 40/70 | 65 | 1.5 | 2.58 | 4.33 | 13.1 |
| Example 11 | 40/70 | 85 | 1.52 | 2.6 | 2.47 | 5.53 |
| Example 12 | 40/70 | 105 | 1.5 | 2.6 | 4.55 | 5.9 |
| Example 13 | 40/70 | 125 | 1.51 | 2.38 | 4.75 | 5.34 |
According to the viscosity change conditions of the resin at different temperatures, the film is coated at the temperature of 85 ℃ in combination with experimental data, and a better effect can be achieved.
Example 14
2 kg of quartz sand particles with the particle size of 425/212 mu m (40/70 meshes) are heated to 250 ℃, put into a sand mixer and stirred, cooled to about 230 ℃, added with 10 g of phenolic resin and stirred for 15 seconds, added with 1.5 g of urotropine and stirred for 20 seconds; adding 10 g of phenolic resin, stirring for 35 seconds, adding 1.5 g of urotropine, stirring for 60 seconds, adding 2 g of calcium stearate, stirring for 90 seconds, cooling and sieving to obtain the traditional resin coated proppant.
| Experiment number | Body weight density (g/ml3) | Optic secret (g/ml3) | Acid soluble (%) | Crushing (48mpa) | Crushing (55mpa) |
| Example 4 | 1.51 | 2.58 | 3.93 | 1.32 | 2 |
| Example 14 | 1.61 | 2.59 | 4.43 | 5.92 | 11 |
Compared with the traditional propping agent, the novel environment-friendly resin has the advantages of low crushing, low density, environmental protection, energy conservation, safety, simple process and the like.
In the process of preparing the proppant:
the aggregates are previously dried to less than 0.5% moisture and preferably less than 0.05.
The aggregate is heated to about 100-150 ℃ and then cooled to 60-120 ℃.
While only the preferred embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. An environment-friendly high-strength resin coated proppant comprises aggregate, environment-friendly resin, a catalyst, a dispersing agent, a drying agent and an anti-blocking agent, and is characterized in that the environment-friendly resin comprises a substance containing a terminal hydroxyl group and a substance containing an isocyanate group, and the weight of the environment-friendly resin is 0.8-1% of the weight of the aggregate;
the catalyst comprises one or a mixture of two or more of organic acid lead and organic tin; the proppant is a pre-cured proppant.
2. The environment-friendly high-strength resin coated proppant as set forth in claim 1, wherein the hydroxyl-terminated substance comprises one or a mixture of two or more of polyols, polyethers, aromatic alcohols, polyesters and castor oil-modified polyols.
3. The environment-friendly high-strength resin coated proppant as set forth in claim 1, wherein the substance containing isocyanate groups comprises one or a mixture of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, polyphenyl polymethylene polyisocyanate, toluene diisohydrocarbonate, hexamethylene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, and tetramethyl m-phenylene diisocyanate.
4. The environment-friendly high-strength resin coated proppant as set forth in claim 1, 2 or 3, wherein the weight ratio of the substance containing terminal hydroxyl groups to the substance containing isocyanate groups is 0.3-5.
5. The environment-friendly high-strength resin coated proppant as set forth in claim 1, wherein the aggregate comprises one or a mixture of two or more of ceramic material, quartz sand particles, walnut shells, resin material, rubber material and glass material.
6. The environment-friendly high-strength resin coated proppant as set forth in claim 1, wherein the anti-blocking agent comprises one or a mixture of two or more of calcium stearate, stearic acid amide, zinc stearate, magnesium stearate, paraffin wax, synthetic paraffin wax, carnauba wax, alkylamide, polyamide, cellulose and calcium carbonate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942334A (en) * | 2012-10-24 | 2013-02-27 | 亿利沙材料科技有限责任公司 | Film-coated modified propping agent, and preparation method and application thereof |
| CN103764945A (en) * | 2011-09-02 | 2014-04-30 | 优选技术有限责任公司 | Dual function proppants |
| CN103889706A (en) * | 2011-07-22 | 2014-06-25 | 优选技术有限责任公司 | Coated and cured proppants |
| CN104039920A (en) * | 2011-12-15 | 2014-09-10 | 阿什兰南方化学科恩弗斯特有限公司 | Method for producing coated proppants |
| CN104520530A (en) * | 2012-01-23 | 2015-04-15 | 优选技术有限责任公司 | Manufacture of polymer coated proppants |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103889706A (en) * | 2011-07-22 | 2014-06-25 | 优选技术有限责任公司 | Coated and cured proppants |
| CN103764945A (en) * | 2011-09-02 | 2014-04-30 | 优选技术有限责任公司 | Dual function proppants |
| CN104039920A (en) * | 2011-12-15 | 2014-09-10 | 阿什兰南方化学科恩弗斯特有限公司 | Method for producing coated proppants |
| CN104520530A (en) * | 2012-01-23 | 2015-04-15 | 优选技术有限责任公司 | Manufacture of polymer coated proppants |
| CN102942334A (en) * | 2012-10-24 | 2013-02-27 | 亿利沙材料科技有限责任公司 | Film-coated modified propping agent, and preparation method and application thereof |
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Address after: 400709 No. 6 Wuxing Middle Road, Tongjiaxi Town, Beibei District, Chongqing Applicant after: Chongqing Changjiang moulding material (Group) Limited by Share Ltd Address before: 401320 Fengqi Road, Caijiagang Town, Beibei District, Chongqing Applicant before: Chongqing Changjiang moulding material (Group) Limited by Share Ltd |
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