CN103849369A - Fracturing propping agent and its preparation method - Google Patents
Fracturing propping agent and its preparation method Download PDFInfo
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- CN103849369A CN103849369A CN201210504068.4A CN201210504068A CN103849369A CN 103849369 A CN103849369 A CN 103849369A CN 201210504068 A CN201210504068 A CN 201210504068A CN 103849369 A CN103849369 A CN 103849369A
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- Prior art keywords
- fracturing propping
- epoxy resin
- contact
- fracturing
- correcting agent
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Abstract
The invention provides a fracturing propping agent preparation method, and a fracturing propping agent prepared through the method. The fracturing propping agent preparation method is characterized in that the fracturing propping agent is obtained by curing a mixture containing aggregate particle particles and a laminating adhesive; and the laminating adhesive is a hydrophilic resin composition, and a preparation method of the hydrophilic resin composition comprises the following steps: allowing an epoxy resin to have first contact with a modifier selected from acid anhydride to make the hydroxy group in the epoxy resin react with the acid anhydride group in the modifier; and allowing a mixture obtained through the first contact to have second contact with an alkaline substance under acid-to-salt conditions. The fracturing propping agent can be well dispersed in a water-based fracturing fluid, the content of bubbles in the water-based fracturing fluid carrying the fracturing propping agent is low, and the fracturing propping agent also has a high crushing limit.
Description
Technical field
The fracturing propping agents that the present invention relates to a kind of preparation method of fracturing propping agents and prepared by the method.
Background technology
In the recovery process of oil and gas, high locking pressure deposits of low permeability is after fracture treatment, Oil gas-containing rock layer is split, the passage that oil gas forms from crack, collect, fracturing propping agents enter Filling in rock crack in company with fracturing liquid, play support crack not stress discharge and closed effect, thereby keep high flow conductivity, make oil gas unimpeded, increase the output of oil and gas.
At present, the more fracturing propping agents of field use are mainly haydite and quartz sand.But the percentage of damage of haydite and quartz sand is high, the haydite crushing in reservoir easily moves, and flow conductivity is poor.The propping agent that adopts the coated particles of aggregates of hydrophobic resin and obtain is widely used in recent years, for example, in the time gathering oil, adopts hydrophobicity resin-coated particles of aggregates and the propping agent that obtains can improve the recovery ratio of oil.
But, in actual application, find, compare as the fracturing liquid of propping agent with quartz sand with carrying using haydite, the fracturing liquid that carries the propping agent obtaining with the coated particles of aggregates of hydrophobic resin need to just can be admitted to underground under higher pumping pressure.
Summary of the invention
Just need to can be admitted to underground problem in order to solve the fracturing liquid that carries the fracturing propping agents that obtain with the coated particles of aggregates of hydrophobic resin under higher pumping pressure; the present inventor conducts in-depth research; find: with adopt haydite or quartz sand as compared with the fracturing liquid of fracturing propping agents; adopt in the fracturing liquid of the coated particles of aggregates of hydrophobic resin as fracturing propping agents; fracturing propping agents agglomeration is obvious, also contains a large amount of bubbles in concurrent fracturing liquid.The existence of the reunion of fracturing propping agents and a large amount of bubbles has increased the difficulty that fracturing liquid is carried, thereby needs higher pumping pressure could the fracturing liquid that carry the fracturing propping agents that obtain with the coated particles of aggregates of hydrophobic resin be sent into underground.
The present inventor finds through great many of experiments; the particles of aggregates that has been coated hydrophilic resin can effectively be solved to fracturing propping agents as fracturing propping agents the problem of reuniting occurs in fracturing liquid; simultaneously can also significantly reduce the bubbles volume in fracturing liquid, this fracturing liquid is admitted under can the pumping pressure even lower at the pumping pressure suitable as the fracturing liquid of fracturing propping agents with adopting haydite or quartz sand underground.Complete on this basis the present invention.
The invention provides a kind of preparation method of fracturing propping agents, the method comprises and will contain the mixture solidified of particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is hydrophilic resin oil/fat composition, and the preparation method of described hydrophilic resin oil/fat composition comprises:
Epoxy resin and at least one properties-correcting agent are carried out to first and contact, described properties-correcting agent is selected from acid anhydrides, and the condition of described the first contact makes the hydroxyl in described epoxy resin react with the anhydride group in described properties-correcting agent; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
The present invention also provides the fracturing propping agents that prepared by aforesaid method.
The fracturing propping agents that are coated on the surface of particles of aggregates by described hydrophilic resin oil/fat composition and obtain are had to good dispersiveness in aqueous fracturing fluid, substantially can not reunite; And it is low to carry air bubble content in the aqueous fracturing fluid of these fracturing propping agents.Therefore, adopt fracturing propping agents prepared by described hydrophilic resin oil/fat composition can under the pumping pressure quite even lower as the fracturing liquid of fracturing propping agents with adopting haydite or quartz sand, be admitted to underground.
In addition, the fracturing propping agents that prepared by described particles of aggregates and hydrophilic resin oil/fat composition also have higher crushing strength, and supporting crack effectively prevents its closure.
Embodiment
The preparation method of fracturing propping agents provided by the invention comprises and will contain the mixture solidified of particles of aggregates and overlay film binding agent, and wherein, described overlay film binding agent is hydrophilic resin oil/fat composition, and the preparation method of described hydrophilic resin oil/fat composition comprises:
Epoxy resin and at least one properties-correcting agent are carried out to first and contact, described properties-correcting agent is selected from acid anhydrides, and the condition of described the first contact makes the hydroxyl in described epoxy resin react with the anhydride group in described properties-correcting agent; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
According to the present invention, described properties-correcting agent is selected from acid anhydrides.When by properties-correcting agent and epoxy resin contact reacts, the hydroxyl containing in anhydride group and epoxy resin molecular structure reacts, and forms carboxylic acid.
Described acid anhydrides is preferably selected from organic acid anhydride, is more preferably selected from aliphatic anhydride, is further preferably selected from C
2-C
12aliphatic anhydride.In molecular structure as the described acid anhydrides of properties-correcting agent, the quantity of anhydride group is generally 1.Particularly, described acid anhydrides can be maleic anhydride, diacetyl oxide, propionic anhydride and Succinic anhydried.In the time that described acid anhydrides contains unsaturated acid anhydride (as maleic anhydride), described the first contact is preferably carried out under the existence of at least one radical polymerization inhibitor, can prevent like this unsaturated group polymerization in unsaturated acid anhydride.Described radical polymerization inhibitor can be for the conventional various materials that can block free radical, for example, as various phenolic compounds (Resorcinol).The consumption of described radical polymerization inhibitor can carry out appropriate selection according to the amount of unsaturated acid anhydride, is not particularly limited.
The hydroxyl value of epoxy resin can be that the routine of this area is selected.Usually, the hydroxyl value of described epoxy resin can be 0.02-0.4mol/100g, more preferably 0.04-0.4mol/100g.Described hydroxyl value can be measured according to the disclosed method in the 3.1-3.3 joint (thermosetting resin, 4:42-45, nineteen ninety-five) of " epoxy resin hydroxyl value measuring method " such as Huang Biwu, in the description of product of the epoxy resin that also can be available commercially, knows.
Epoxy group(ing) in described epoxy resin is mainly used in reacting with solidifying agent, to form the product with some strength.The amount of the epoxy group(ing) in epoxy resin is not particularly limited, and can be conventional selection.Usually, the oxirane value of described epoxy resin can be 0.2-0.6mol/100g.
According to the present invention, the amount of the carboxyl that the consumption of described properties-correcting agent can be introduced according to expection in epoxy resin molecular structure is carried out appropriate selection.In the preparation process of described fracturing propping agents, described properties-correcting agent is in the total amount of anhydride group, and the hydroxyl in described epoxy resin and the mol ratio of described properties-correcting agent can be 1:0.1-0.8, are preferably 1:0.3-0.7.
According to the present invention, epoxy resin carries out with contacting under the first contact conditions of described properties-correcting agent.The present invention is not particularly limited for described the first contact conditions, as long as the condition of described the first contact is enough to make the anhydride group in hydroxyl and the described properties-correcting agent in epoxy resin to react.Usually, described the first contact can be carried out at the temperature of 60-120 ℃.Preferably, described the first contact is carried out at the temperature of 70-110 ℃.The time of described the first contact can, according to carrying out the temperature of the first contact and the concrete kind of properties-correcting agent is carried out appropriate selection, be not particularly limited, and can be generally 1-10 hour.Described the first contact can be at acidic conditions (for example; PH value is 2-4) under carry out.
According to the present invention, at least one alkaline matter is contacted to the mixture obtaining under the condition that is enough to make acid formation salt carry out the second contact with first, described alkaline matter can contact and the carboxyl reaction that forms in epoxy resin molecular structure with by first, forms salt.
Described alkaline matter can be various can reacting with carboxyl, and the hydrogen ion in carboxyl is replaced by other positively charged ion, thereby forms the material of salt.For example, described alkaline matter can be selected from tertiary amine and/or M (OH)
2, wherein, M is selected from alkali and alkaline earth metal ions, and n is 1 or 2.
Described tertiary amine preferably as shown in the formula (I),
In formula (I), R
1, R
2and R
3c respectively does for oneself
1-C
5straight or branched alkyl.
Described C
1-C
5the specific examples of straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
M (OH)
nin M be preferably basic metal (as Na or K), more preferably Na, n is 1.
Particularly, described alkaline matter can be selected from Trimethylamine 99, triethylamine, tripropyl amine and isomer thereof, Tributylamine and isomer thereof, sodium hydroxide and potassium hydroxide.
According to the present invention, the amount of described alkaline matter can be carried out appropriate selection according to the amount of carboxyl and the hydrophilicity of expection introduced in epoxy resin by the first contact.In the preparation process of described fracturing propping agents, described properties-correcting agent is in the total amount of anhydride group, and the mol ratio of described alkaline matter and described properties-correcting agent can be 0.4-1:1, is preferably 0.5-1:1.
According to the present invention, described the second contact is carried out under the condition that is enough to make acid formation salt.The condition of described the second contact can be conventional selection, if described alkaline matter can with epoxy resin molecular structure in carboxyl formation salt.Particularly, described the second contact can be carried out at the temperature of 25-50 ℃.The time of described the second contact can be carried out appropriate selection according to the temperature of the second contact, is not particularly limited, and can be generally 0.5-5 hour.
According to the present invention, described the first contact contacts with second preferably to be carried out under the existence of at least one solvent, can regulate the severe degree of reaction more easily so on the one hand, can also make on the other hand the contact of each reactant more abundant.Described solvent can be for the various epoxy resin that can either dissolve as matrix resin, liquid that again can soluble modified dose.Particularly, described solvent can be selected from toluene, butanols (comprising the various isomer of butanols, as 1-propyl carbinol and the trimethyl carbinol), butyl glycol ether (comprising ethylene glycol monobutyl ether and ethylene glycol bis butyl ether) and butanone.
The consumption of described solvent can be conventional selection.Usually, with respect to 100 weight part epoxy resin, the consumption of described solvent can be 50-200 weight part.
According to the present invention, described the first contact contacts with described second while carrying out under the existence of at least one solvent, and method of the present invention also comprises the solvent removing in the mixture that the second contact obtains.Can adopt the conventional the whole bag of tricks in this area to remove described solvent, for example: underpressure distillation.
According to the present invention, described particles of aggregates can be the existing various particulate materials of preparing fracturing propping agents that can be used in, and for example, described particles of aggregates can be selected from one or more in roughing sand, slag, haydite and glass microballon.Wherein, described roughing sand can be both natural silica Sand, can be also artificial silica sand.Described natural silica Sand can be river sand, extra large sand and aeolian sand, is preferably the aeolian sand from desert.
According to the present invention, the mean diameter of described particles of aggregates can in very large range change, and can reasonably select according to actual needs, for example, the mean diameter of described particles of aggregates can be 0.04-5 millimeter, is preferably 0.05-2 millimeter, more preferably 0.1-0.85 millimeter.The mean diameter of described particles of aggregates is to adopt method of sieving to measure., make particles of aggregates measure its mean diameter by the sieve aperture of different size.
According to the present invention, the degree of sphericity of described particles of aggregates can be selected and change in wider scope, and as a rule, degree of sphericity is better, and the flow conductivity after fragmentation is stronger, and therefore, under preferable case, the circularity of described particles of aggregates and sphericity are preferably >=0.6.Wherein, " sphericity " refers to the degree of particle subglobular; " circularity " refers to the relative acutance of grain corner or measuring of curvature.The measuring method of sphericity and circularity is conventionally known to one of skill in the art, for example, can adopt chart method to measure.
According to the present invention, the content of described particles of aggregates and overlay film binding agent can be selected and change in wider scope, and for example, with respect to particles of aggregates described in 100 weight parts, the amount of described overlay film binding agent can be 1-10 weight part, is preferably 2-8 weight part.
According to the present invention, in the preparation process of described fracturing propping agents, can also optionally add epoxy curing agent according to practical situation.Particularly, described epoxy curing agent can be selected from conventional various amine curing agent and/or the acid anhydride type curing agents that can make epoxy resin generation crosslinking reaction, its specific examples can include but not limited to: Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, Benzophenone carboxylic acid dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, alkylene Succinic anhydried, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, norbornene dicarboxylic anhydride, Pyroglutaric acid, terpenes acid anhydrides, methyl cyclohexene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, poly-nonane diacid acid anhydride, poly sebacic polyanhydride, PHT4, tetrachlorophthalic anhydride, trimellitic anhydride glycol ester, trimellitic anhydride glyceryl ester, sulfobenzide tetracarboxylic dianhydride, quadrol, diethylenetriamine, two amido sulfobenzides, two amido ditanes, mphenylenediamine, Dyhard RU 100, polyetheramine, diethylenetriamine, hexanediamine, trimethylhexamethylenediamine and tetraethylene pentamine.Preferably, described epoxy curing agent is selected from tetrahydrophthalic anhydride, HHPA, two amido ditanes, diethylenetriamine and Dyhard RU 100.
The consumption of described epoxy curing agent can carry out appropriate selection according to its kind, so that the epoxy resin in described hydrophilic resin oil/fat composition can solidify, and the fracturing propping agents that make finally to obtain have certain intensity and are as the criterion.Usually, the consumption of described epoxy curing agent can be this solidifying agent theoretical consumption 0.9-1.2 doubly.Can adopt known the whole bag of tricks to determine the theoretical consumption of solidifying agent.For example, in the time that described epoxy curing agent is amine curing agent, can calculate its theoretical consumption by following formula:
W=(M/H
n)×E，
Wherein, W is the quality of the needed solidifying agent of every 100g epoxy resin, g;
M is the molecular weight of solidifying agent;
H
nfor the number of reactive hydrogen on amido in each solidifying agent molecule;
E is the oxirane value of epoxy resin, mol/100g.
Again for example, in the time that described epoxy curing agent is acid anhydride type curing agent, can calculate by following formula the theoretical consumption of solidifying agent:
W=A
E×E×K，
Wherein, W is the quality of the needed solidifying agent of every 100g epoxy resin, g;
A
efor the molecular weight of acid anhydrides;
E is the oxirane value of epoxy resin, mol/100g;
K is an empirical value within 0.5-1.1, is generally 0.85.
According to the present invention, described curing condition can be that the routine of this area is selected, and as a rule, described curing condition can comprise solidification value and set time.Described solidification value can suitably be selected according to the kind of the solidifying agent of selecting, and as a rule, in the time that described curing temperature is 100-250 ℃, just can make described solidifying carry out smoothly.As a rule, the prolongation of described set time is conducive to solidify more completely, but set time, the long amplitude that state of cure is improved was also not obvious, therefore, considered effect and efficiency, was preferably 0.05-0.5 hour described set time.
From avoiding between particles of aggregates the angle of bonding mutually, be solidificated under the condition of following stirring described in preferably and carry out.
The present invention also provides the fracturing propping agents that prepared by aforesaid method.
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, according to the method stipulating in SY/T5108-2006, the percentage of damage of fracturing propping agents is measured.
Embodiment 1-3 is for illustrating according to hydrophilic resin composition and method of making the same of the present invention and application.
Embodiment 1
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-21, and oxirane value is 0.21mol/100g, and hydroxyl value is 0.226mol/100g) be dissolved in 50g toluene, add 0.003g Resorcinol, the pH value of reaction solution is adjusted to 2.Follow to stir temperature is increased to 100 ℃, then add 9.8g MALEIC ANHYDRIDE, stirring reaction 2 hours at this temperature; Then be cooled to 40 ℃, add 10.1g triethylamine, continue reaction after 0.5 hour, by the mixture obtaining Rotary Evaporators evaporating solvent, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat composition 100g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 25g tetrahydrophthalic anhydride and 3g diethylenetriamine, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The crush resistance of these fracturing propping agents can be listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare fracturing propping agents, different, the epoxy resin using by embodiment 1 step (1) replaces the hydrophilic resin oil/fat composition in embodiment 1 step (2).The crush resistance of the fracturing propping agents that obtain can be listed in table 1.
Fracturing propping agents prepared by 5g comparative example 1 drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are reunited in sinking process, and in sinking process and be deposited on many and large (for being greater than 3mm) of diameter of the bubble on fracturing propping agents surface of graduated cylinder bottom.Showing to carry the fracturing liquid of these fracturing propping agents just can be admitted under need to the pumping pressure larger at the fracturing liquid than carrying haydite underground.
Embodiment 2
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-51, and oxirane value is 0.51mol/100g, and hydroxyl value is 0.046mol/100g) be dissolved in 50g toluene, add 0.001g Resorcinol, the pH value of reaction solution is adjusted to 4.Follow to stir temperature is increased to 100 ℃, then add 3.0g MALEIC ANHYDRIDE, stirring reaction 3 hours at this temperature; Then cool the temperature to 50 ℃, add 4.3g Tri-n-Propylamine, continue reaction after 0.5 hour, by the mixture obtaining Rotary Evaporators evaporating solvent, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat composition 100g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 30 2 amido ditanes, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The crush resistance of these fracturing propping agents can be listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Embodiment 3
(1) 100g epoxy resin (be purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-44, and oxirane value is 0.44mol/100g, and hydroxyl value is 0.088mol/100g) is dissolved in 50g toluene, the pH value of reaction solution is adjusted to 3.Follow to stir temperature is increased to 95 ℃, then add 5g Succinic anhydried, stirring reaction 4 hours at this temperature; Then cool the temperature to 50 ℃, add 9.3g tri-n-butylamine, continue reaction after 0.5 hour, by evaporating solvent in Rotary Evaporators for the mixture obtaining, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat composition 160g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 35g tetrahydrophthalic anhydride and 3g Dyhard RU 100, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The performance of these fracturing propping agents is listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Table 1
Wherein, " percentage of damage " refers to the propping agent to certain volume, carries out pressure-bearing test under rated pressure, and definite percentage of damage has characterized the ability of the anti-fragmentation of propping agent.
Can find out from embodiment 1-3 and comparative example 1, the fracturing propping agents of being prepared by described hydrophilic resin oil/fat composition have good dispersibility in water, and the air bubble content in the water that contains fracturing propping agents of the present invention is low, show that the fracturing liquid that carries the fracturing propping agents of being prepared by described hydrophilic resin oil/fat composition is easy to pumping, can with carry under the basic identical even less pressure of fracturing liquid of haydite as propping agent, be pumped to underground.Meanwhile, the fracturing propping agents of being prepared by described hydrophilic resin oil/fat composition also have higher crushing strength, and effectively support fracturing crack, prevents its closure.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for fracturing propping agents, the method comprises containing the mixture solidified of particles of aggregates and overlay film binding agent, it is characterized in that, described overlay film binding agent is hydrophilic resin oil/fat composition, and the preparation method of described hydrophilic resin oil/fat composition comprises:
Epoxy resin and at least one properties-correcting agent are carried out to first and contact, described properties-correcting agent is selected from acid anhydrides, and the condition of described the first contact makes the hydroxyl in described epoxy resin react with the anhydride group in described properties-correcting agent; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
2. method according to claim 1, wherein, described properties-correcting agent is in the total amount of anhydride group, and the hydroxyl in described epoxy resin and the mol ratio of described properties-correcting agent are 1:0.1-0.8.
3. method according to claim 1, wherein, described properties-correcting agent is in the total amount of anhydride group, and the mol ratio of described alkaline matter and described properties-correcting agent is 0.4-1:1.
4. according to the method described in any one in claim 1-3, wherein, described properties-correcting agent is selected from C
2-C
12aliphatic anhydride, be preferably selected from maleic anhydride, diacetyl oxide, propionic anhydride and Succinic anhydried.
5. according to the method described in claim 1 or 3, wherein, described alkaline matter is selected from tertiary amine and/or M (OH)
n, M is selected from alkali and alkaline earth metal ions, and n is 1 or 2;
Described tertiary amine preferably as shown in the formula (I),
In formula (I), R
1, R
2and R
3c respectively does for oneself
1-C
5straight or branched alkyl;
M (OH)
nin M be preferably basic metal, n is 1; M is Na more preferably.
6. method according to claim 1 and 2, wherein, the hydroxyl value of described epoxy resin is 0.02-0.4mol/100g, the oxirane value of described epoxy resin is preferably 0.2-0.6mol/100g.
7. method according to claim 1, wherein, described the first contact is carried out at the temperature of 60-120 ℃, and described the second contact is carried out at the temperature of 25-50 ℃.
8. method according to claim 1, wherein, the circularity of described particles of aggregates and sphericity >=0.6.
9. method according to claim 1, wherein, described curing condition comprises that solidification value is 100-250 ℃, be 0.05-0.5 hour set time.
10. the fracturing propping agents that in claim 1-9, the method described in any one prepares.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210504068.4A CN103849369A (en) | 2012-11-30 | 2012-11-30 | Fracturing propping agent and its preparation method |
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|---|---|---|---|
| CN201210504068.4A CN103849369A (en) | 2012-11-30 | 2012-11-30 | Fracturing propping agent and its preparation method |
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Cited By (3)
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| CN105623638A (en) * | 2014-10-31 | 2016-06-01 | 中国石油天然气股份有限公司 | Resin coated hollow glass beads and preparation method therefor |
| CN106867500A (en) * | 2016-12-31 | 2017-06-20 | 北京晨础石油科技有限公司 | Overlay film proppant and preparation method thereof |
| CN110423604A (en) * | 2019-09-06 | 2019-11-08 | 西南石油大学 | Sand control proppant and its preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623638A (en) * | 2014-10-31 | 2016-06-01 | 中国石油天然气股份有限公司 | Resin coated hollow glass beads and preparation method therefor |
| CN106867500A (en) * | 2016-12-31 | 2017-06-20 | 北京晨础石油科技有限公司 | Overlay film proppant and preparation method thereof |
| CN106867500B (en) * | 2016-12-31 | 2019-12-31 | 北京晨础石油科技有限公司 | Tectorial membrane proppant and preparation method thereof |
| CN110423604A (en) * | 2019-09-06 | 2019-11-08 | 西南石油大学 | Sand control proppant and its preparation method and application |
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