WO2018176532A1 - 交联剂、全悬浮压裂液及其制备方法 - Google Patents

交联剂、全悬浮压裂液及其制备方法 Download PDF

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WO2018176532A1
WO2018176532A1 PCT/CN2017/081240 CN2017081240W WO2018176532A1 WO 2018176532 A1 WO2018176532 A1 WO 2018176532A1 CN 2017081240 W CN2017081240 W CN 2017081240W WO 2018176532 A1 WO2018176532 A1 WO 2018176532A1
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fracturing fluid
crosslinking agent
reaction
fully suspended
salt
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PCT/CN2017/081240
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English (en)
French (fr)
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任山
张绍彬
寇将
唐朝钧
王梦莹
康毅
高礼鑫
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成都劳恩普斯科技有限公司
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Publication of WO2018176532A1 publication Critical patent/WO2018176532A1/zh

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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
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/26—Gel breakers other than bacteria or enzymes

Definitions

  • the invention relates to the technical field of oil and gas field exploitation, and in particular to a crosslinking agent, a full suspension fracturing fluid and a preparation method thereof.
  • Fracturing is a process technology for transforming the seepage characteristics of oil reservoirs. It is an important technological measure for increasing production and increasing injection of oil and gas wells.
  • Reservoir reform is one of the main measures to increase oil and gas wells.
  • Fracturing fluid is the main liquid in reservoir reformation.
  • the fracturing fluid uses the ground high-pressure pumping group to inject into the well with a displacement exceeding the absorption capacity of the formation, forming a high pressure near the bottom of the well. After this pressure exceeds the formation stress near the bottom of the well and the tensile strength of the rock, a crack is formed in the formation.
  • the fracturing fluid carries the proppant into the crack. When the fracturing fluid breaks back into the discharge, the proppant is left in the crack to improve the conductivity of the oil and gas layer.
  • the ability to carry proppants is a key performance indicator for fracturing fluids and plays a vital role in fracturing stimulation.
  • the full suspension fracturing fluid has better temperature resistance, shear resistance and sand carrying capacity, can solve the problem that the proppant settles under the crack, and realizes that the proppant is more evenly laid in the longitudinal direction of the crack, and can effectively transport the proppant. Go further to the crack and get a longer length of sand fill crack. Good proppant carrying capacity will help to improve the placement efficiency of the proppant in the horizontal and longitudinal directions of the crack.
  • the effective support crack half length and the longitudinal support height are greatly improved;
  • the same effective crack half length or crack support area, the amount of proppant and liquid is greatly reduced, and the cost is also greatly reduced, so the better the effect of carrying the proppant is, the better the yield increase effect of the fracturing fluid is. It is important to study the fracturing fluid with strong sand carrying capacity to transform the reservoir.
  • the object of the present invention is to provide a crosslinking agent which can be reacted with a thickening agent to obtain a fracturing fluid having a full suspension function, which can be applied to oil and gas well fracturing.
  • Another object of the present invention is to provide a method for preparing a crosslinking agent, and the crosslinking agent prepared by the method has superior crosslinking ability.
  • Another object of the present invention is to provide a fully suspended fracturing fluid prepared by a thickening agent and the above cross-linking agent, which has better temperature and shear resistance and can solve the conventional pressure.
  • the problem of rapid sedimentation of the cracking proppant, the use of the fully suspended fracturing fluid can achieve proppant close to zero settling, obtain a better longitudinal support profile and half length of the crack, contribute to the increase of oil and gas wells, and can reduce the proppant Use, reduce costs.
  • Another object of the present invention is to provide a method for preparing a fully suspended fracturing fluid.
  • the fully suspended fracturing fluid prepared by the preparation method can achieve proppant close to zero sedimentation and has better sand carrying property.
  • the crosslinking agent according to the present invention is mainly produced from the following components in parts by weight: 6 to 10 parts of the water-soluble high-valent metal salt, 10 to 14 parts of the polyhydric alcohol, or a carboxylic acid or a salt thereof 4 to 8 servings.
  • the water-soluble high-valent metal salt includes aluminum citrate, aluminum trichloride, aluminum sulfate, zirconium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium acetate, zirconium nitrate, zirconium carbonate, One or more of ammonium zirconium carbonate.
  • the polyol includes ethylene glycol, polyethylene glycol, glycerin, propylene glycol, 1,4-butanediol, mannitol, triethylene glycol, xylitol, and triethanolamine. One or more.
  • the carboxylic acid includes one or more of formic acid, acetic acid, glycolic acid, lactic acid, citric acid, tartaric acid, and gluconic acid.
  • the carboxylate salt includes one or more of formic acid, acetic acid, glycolic acid, lactic acid, citric acid, sodium or potassium salt of gluconic acid, and sodium tartrate.
  • the crosslinking agent further includes 3 to 15 parts of an inorganic salt, and the inorganic salt includes one or more of a sodium salt, a potassium salt, a magnesium salt, and a calcium salt.
  • the invention also provides a preparation method of a crosslinking agent, comprising the steps of dispersing a water-soluble high-valent metal salt, a polyhydric alcohol, a carboxylic acid or a salt thereof in a solvent to obtain a reaction liquid, and reacting the reaction liquid under heating and acidic conditions. .
  • the method for reacting the reaction liquid under heating and acidic conditions comprises the steps of adjusting the pH of the reaction liquid to 4 to 7, and heating to carry out the reaction.
  • the pH of the reaction solution is adjusted by using a pH adjusting agent, and the pH adjusting agent comprises one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate or A variety.
  • the reaction temperature of the reaction solution is from 40 to 90 ° C under the conditions of a pH of 4 to 7.
  • the reaction time of the reaction solution is 3 to 8 hours under the conditions of a pH of 4 to 7 and a reaction temperature of 40 to 90 °C.
  • an inorganic salt is further added to continue the reaction.
  • the reaction is continued for 20 to 40 minutes.
  • the reaction liquid in the step of heating the reaction liquid, is stirred under a stirring rate of 50 to 100 r/min.
  • the present invention also provides a fully suspended fracturing fluid comprising cross-linking a thickening agent with the above crosslinking agent to form a crosslinked product having a spatial network structure.
  • the thickening agent comprises a polyacrylamide-based polymer.
  • a hydrophobic monomer is introduced into the molecular chain of the polyacrylamide-based polymer.
  • the crosslinking agent is complexed with a metal ion capable of forming a crosslinking reaction with the polyacrylamide-based polymer.
  • the polyacrylamide-based polymer has a molecular weight of greater than or equal to 5 million.
  • the fully suspended fracturing fluid is a dispersion system in which water is a dispersing agent.
  • the fully suspended fracturing fluid of the present invention further includes an additive.
  • the additive includes at least one of an anti-swelling agent, a drainage aid, and a viscosity-retaining agent.
  • the viscosity retaining agent includes at least one of a non-oxidizing bactericide and a reducing agent.
  • the non-oxidizing bactericide comprises one of glutaraldehyde, dodecyltrimethylbenzylammonium chloride, isothiazolinone, and benzisothiazolinone. Or a variety.
  • the reducing agent includes one or more of thiourea, sodium thiosulfate, sodium sulfite, sodium hydrogensulfite, and potassium iodide.
  • the fully suspended fracturing fluid according to the present invention is mainly made up of the following components in mass percentage: 0.2 to 0.5% of the thickening agent, 0.3 to 0.8% of the crosslinking agent, 0.05 to 1.3% The additive and the balance of water.
  • the mass percentage of the anti-swelling agent in the fully suspended fracturing fluid is 0.1 to 0.5%, and the mass percentage of the drainage aid in the fully suspended fracturing fluid
  • the mass percentage of the viscosity retaining agent in the fully suspended fracturing fluid is from 0.05 to 0.3%, and is from 0.1 to 0.5%.
  • the settling velocity of the proppant in the fully suspended fracturing fluid is less than 2 mm/h.
  • the invention also provides a preparation method of a full suspension fracturing fluid, comprising: crosslinking a thickening agent with the above crosslinking agent.
  • the thickening agent is mixed with an additive before the thickening agent is crosslinked with the crosslinking agent.
  • the beneficial effects of the cross-linking agent, the fully-suspended fracturing fluid and the preparation method thereof in the embodiments of the present invention are: reacting a water-soluble high-valent metal salt, a polyhydric alcohol, a carboxylic acid or a salt thereof to prepare a cross-linking agent having good crosslinkability .
  • the cross-linking agent and the polyacrylamide thickener cross-link to form a dense spatial network structure, so that the prepared full-suspended fracturing fluid has good temperature resistance and superior sand-carrying property, and can be applied to high-temperature stratum on the other hand.
  • the sedimentation speed of the proppant is close to zero, and it maintains the full suspension state during the transportation process, which can effectively solve the problem of rapid sedimentation of the proppant, reduce the amount of proppant, reduce the cost, and bring a good economy. benefit.
  • Example 1 is a test chart of rheological properties of a fully suspended fracturing fluid according to Example 26 of the present invention
  • Example 2 is a comparison diagram of static sand-carrying performance of a fully suspended fracturing fluid of Example 26, a polymer fracturing fluid of Comparative Example 1, and a silicone fracturing fluid of Comparative Example 2;
  • FIG. 3 is a comparison diagram of dynamic sand-carrying performance of a fully suspended fracturing fluid, a polymer fracturing fluid of Comparative Example 1, and a silicone fracturing fluid of Comparative Example 2 at 25 ° C according to Example 26 of the present invention;
  • Example 4 is a comparison diagram of dynamic sand-carrying performance of a fully suspended fracturing fluid, a polymer fracturing fluid of Comparative Example 1, and a silicone fracturing fluid of Comparative Example 2 at 90 ° C according to Example 26 of the present invention.
  • cross-linking agent the full suspension fracturing fluid and the preparation method thereof according to the examples of the present invention are specifically described below.
  • the cross-linking agent provided by the embodiment of the invention is mainly prepared from the following components by weight: 6-12 parts of water-soluble high-valent metal salt, 8-16 parts of polyhydric alcohol, carboxylic acid or its salt 4 ⁇ 10 copies.
  • the water-soluble high-valent metal salt is 6 to 10 parts
  • the polyol is 10 to 14 parts
  • the carboxylic acid or a salt thereof is 4 to 8 parts.
  • the water-soluble high-valent metal salt is a salt of a cation as a heavy metal such as copper, lead, zinc, iron, cobalt, nickel or the like.
  • the metal salt ionizes in water and hydrates to form a hydrated complex ion, which can be crosslinked with the thickening agent.
  • the water-soluble high-valent metal salt comprises aluminum citrate, aluminum trichloride, aluminum sulfate, zirconium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium acetate, zirconium nitrate, carbonic acid One or more of zirconium and ammonium zirconium carbonate.
  • the polyol comprises ethylene glycol, polyethylene glycol, glycerol, propylene glycol, 1,4-butanediol, mannitol, triethylene glycol, xylitol, three One or more of ethanolamines.
  • the carboxylate salt comprises one or more of formic acid, acetic acid, glycolic acid, lactic acid, citric acid, sodium or potassium salt of gluconic acid, and sodium tartrate.
  • the crosslinking agent further includes an inorganic salt
  • the inorganic salt includes one or more of a sodium salt, a potassium salt, a magnesium salt, and a calcium salt.
  • the inorganic salt may be selected from sodium chloride, potassium chloride, magnesium sulfate or the like.
  • the invention also provides a preparation method of the above cross-linking agent, comprising:
  • water is used as a reaction solvent; in order to uniformly and fully dissolve the reactant in water, the water-soluble high-valent metal salt and the polyol are slowly stirred at a stirring rate of 50 to 150 r/min. Add to the water in turn.
  • the rate of slowly adding the water-soluble high-valent metal salt or polyol is 2 to 4 kg/min, and preferably, the rate of adding the water-soluble high-valent metal salt or polyol is 3 kg/min.
  • the mixture was thoroughly stirred to completely dissolve the reactants. Specifically, the stirring time is 10 to 20 minutes, and the stirring time is 15 minutes.
  • the carboxylic acid or its salt is continuously added to ensure uniform mixing.
  • the rate of addition of the carboxylic acid or a salt thereof is 3 to 5 kg/min, and preferably, the rate of addition of the carboxylic acid or a salt thereof is 4 kg/min.
  • the pH of the reaction between the different metal ions and the ligand is different, it is necessary to adjust the pH of the reaction liquid to make it suitable for the formation of a crosslinking agent, and to make the crosslinking agent have good crosslinkability.
  • the pH adjusting agent is slowly added to make the reaction liquid acidic, and the pH of the reaction liquid is preferably 4 to 7. After heating, the reaction is carried out, and then an inorganic salt is added for the reaction. .
  • the reaction solution After adjusting the pH of the reaction solution, the reaction solution is heated to reach the temperature required for the reaction for the first reaction, the reaction temperature is 40 to 90 ° C, and the reaction time is 3 to 8 hours.
  • the reaction temperature is 40 to 90 ° C
  • the reaction time is 3 to 8 hours.
  • the stirring contributes to the formation of the crosslinking agent.
  • the stirring is carried out at a stirring rate of 50 to 100 r/min.
  • the stirring rate is 75 r/min.
  • the obtained product is a crosslinking agent.
  • the reactant undergoes a coordination complexation reaction to obtain a crosslinking agent which can produce a polyhydroxy bridge structure.
  • the crosslinking agent is organic zirconium.
  • Organic zirconium as a cross-linking agent has obvious slow cross-linking characteristics, which is beneficial to the time-dependent control of fracturing fluid viscosity, obtaining higher crack length and improving fracturing effect.
  • Embodiments of the present invention also provide a fully suspended fracturing fluid comprising crosslinking a thickening agent with the above crosslinking agent to form a crosslinked product having a spatial network.
  • the thickening agent is a high molecular polymer.
  • the thickener and the cross-linking agent are cross-linked, the thickener has a cross-linking point, and the lone pair of electrons at the cross-linking point can coordinate with the atomic orbital to form an intermolecular and intramolecular complex bond, thereby forming a space. Network structure.
  • the thickening agent comprises a polyacrylamide-based polymer.
  • the polyacrylamide-based polymer is a water-soluble high molecular polymer.
  • the polyacrylamide solution can be regarded as a network structure, and physical entanglement and hydrogen bonding between the chains form a network node.
  • the interaction between the molecular chains is strengthened, and the hydrodynamic volume is increased. Large, showing a higher viscosity, so it is used as a thickener.
  • a hydrophobic monomer is introduced into the molecular chain of the polyacrylamide-based polymer.
  • hydrophobic monomer into a polyacrylamide-based polymer is because, in an aqueous solution, the hydrophobic groups of the polymer are aggregated due to hydrophobic interaction, and the macromolecules are in-chain and intermolecularly associated.
  • the polymer concentration is higher than a certain critical concentration, the macromolecular chains are aggregated by hydrophobic association to form a supramolecular structure dominated by intermolecular association-dynamic physical cross-linking network, the hydrodynamic volume is increased, and the solution viscosity is large. The amplitude increases.
  • the crosslinking agent is complexed with a metal ion which forms a crosslinking reaction with the polyacrylamide-based polymer.
  • the prepared crosslinking agent is hydrated and hydrolyzed in the solution to form a multinuclear hydroxy bridge ion, which is crosslinked with the polyacrylamide to further enhance the spatial network structure and form a dense network. structure.
  • the thickener has a large molecular weight, the macromolecular chains aggregate to form a network structure, the hydrodynamic volume increases, and the solution viscosity increases greatly.
  • the polyacrylamide-based polymer has a molecular weight of greater than or equal to 5 million.
  • the fully suspended fracturing fluid is a dispersion of water as a dispersing agent.
  • the fully suspended fracturing fluid further comprises an additive.
  • the additive comprises at least one of an anti-swelling agent, a drainage aid, and a viscosity retention agent.
  • Clay minerals generally exhibit electronegativity and are highly hydrated.
  • the anti-swelling agent neutralizes the negative charge of the clay surface, thereby preventing the expansion of the clay.
  • the anti-swelling agent may be selected from potassium chloride or other reagents.
  • the drainage aid can reduce the surface tension of the fracturing fluid or the interfacial tension of the oil-water interface, and reduce the capillary resistance encountered when the fracturing fluid returns to the discharge.
  • the use of a drainage aid can increase the fracturing fluid return rate and shorten the drainage time.
  • the drainage aid is a hydrocarbon surfactant, and in other embodiments of the invention, the drainage agent may be a fluorocarbon surfactant.
  • the viscosity retaining agent is used for preventing the viscosity of the fracturing fluid from being lowered, maintaining the viscosity of the fracturing fluid, and having good sand carrying property.
  • the viscosity retaining agent is at least one of a non-oxidizing bactericide and a reducing agent.
  • the viscosity retaining agent may be a reducing substance such as thiourea, sodium thiosulfate, sodium sulfite, sodium hydrogen sulfite or potassium iodide, and inhibits hydrolysis and oxidation of the polymer. Especially in the presence of iron and ferrous ions, it is more necessary to add in order to maintain the performance of the polymer solution.
  • the viscosity retaining agent may also be a non-oxidizing bactericide such as glutaraldehyde, dodecyltrimethylbenzylammonium chloride, isothiazolinone or benzisothiazolinone, and a non-oxidizing bactericide for preventing the aqueous polymer solution.
  • a non-oxidizing bactericide such as glutaraldehyde, dodecyltrimethylbenzylammonium chloride, isothiazolinone or benzisothiazolinone, and a non-oxidizing bactericide for preventing the aqueous polymer solution.
  • the fully suspended fracturing fluid is mainly made of the following components in mass percentage: 0.2 to 0.5% thickening agent, 0.3 to 0.8% crosslinking agent, 0.05 to 1% additive and the balance of water.
  • the mass percentage of the anti-swelling agent in the fully-suspended fracturing fluid is 0.1 to 0.5%
  • the mass percentage of the drainage aid in the fully-suspended fracturing fluid is 0.1 to 0.5%
  • the mass percentage of the viscosity retaining agent in the fully suspended fracturing fluid is 0.05 to 0.3%.
  • ammonium persulfate can be added as a gel breaker during construction, and in the preferred embodiment of the present invention, at 90 degrees Celsius, when the amount of ammonium persulfate is 100 ppm,
  • the viscosity of the breaker is controlled to be less than 5 mPa ⁇ s in 2 hours.
  • Sand carrying capacity is one of the important indicators to evaluate the performance of fracturing fluid. Further, in a preferred embodiment of the invention, the settling rate of the proppant in the fully suspended fracturing fluid is less than 2 mm/h.
  • the sand ratio can be 3% to 50%
  • the proppant can be selected from quartz sand, ceramsite, and resin coated sand
  • the particle size of the proppant can be 5 to 10 mesh. 10 to 20 mesh, 20 to 40 mesh, 30 to 50 mesh, 40 to 70 mesh, and the like.
  • the invention also provides a preparation method of the above full suspension fracturing fluid, comprising:
  • the thickening agent is dissolved in water under stirring, and stirring is continued after the addition is completed.
  • the stirring time is 10 to 20 minutes;
  • the crosslinking agent is added under continuous stirring, and the crosslinking reaction is completed to obtain a full suspension fracturing fluid.
  • Water-soluble high-valent metal salt 5 parts of zirconium oxychloride
  • Polyol 8 parts of mannitol
  • Carboxylic acid or its salt 4 parts of sodium citrate
  • pH adjuster 1 part of sodium carbonate
  • Inorganic salt 3 parts of potassium chloride
  • Solvent 80 parts of water.
  • the preparation method of the crosslinking agent includes:
  • the mixed salt was a mixture of aluminum citrate, zirconium oxychloride, and aluminum trichloride in a molar mass ratio of 1:1:1.
  • the mixed alcohol is a mixture of glycerol, mannitol, and ethylene glycol in a molar mass ratio of 1:1:1.
  • the mixture was a mixture of acetic acid, glycolic acid, and sodium lactate in a molar mass ratio of 1:1:1.
  • the mixed inorganic salt is a mixture of sodium chloride, potassium chloride and calcium chloride in a molar mass ratio of 1:1:1.
  • Thickener 0.2% modified polyacrylamide
  • Crosslinking agent 0.3% of the crosslinking agent of Example 1;
  • Anti-swelling agent 1% potassium chloride
  • Viscosity retention agent 0.05% thiourea
  • the preparation method of the full suspension fracturing fluid includes:
  • the polymer fracturing fluid provided in this comparative example was prepared by the following preparation method, which includes:
  • the silicone fracturing fluid provided in the present comparative example is prepared by the following preparation method, which includes:
  • hydroxypropyl tantalum gum 0.4 wt% of hydroxypropyl tantalum gum was added to the water and stirred for 30 minutes, 0.15 wt% of sodium carbonate was added thereto and stirring was continued for 10 minutes to obtain a homogeneous viscous liquid, 1 wt% of potassium chloride, 0.3 wt%.
  • Glutaraldehyde and 0.4% by weight of a crosslinking agent are dissolved in an aqueous solution and stirred uniformly to obtain a water-based silicone fracturing fluid.
  • Example 14 Viscosity (mPa ⁇ s) Example 14 32 Example 15 31 Example 16 43 Example 17 36 Example 18 35 Example 19 41 Example 20 56 Example 21 30 Example 22 49 Example 23 54 Example 24 33 Example 25 40 Example 26 60 Comparative example 1 36 Comparative example 2 53
  • the fracturing fluid has a higher viscosity.
  • the fully suspended fracturing fluid of Example 26 was cross-linked with the modified polyacrylamide as a thickening agent and the crosslinking agent of Example 13 (the main component was organic zirconium), and the organic zirconium was hydrated, hydrolyzed and hydroxylated in the solution. Bridge formation The hydroxy bridge ion cross-links with polyacrylamide to enhance the strength of the space network structure, so that the fully suspended fracturing fluid prepared has a good viscosity.
  • the rheological properties of the fully suspended fracturing fluid of Example 26 were tested to test its temperature and shear resistance. Using a HAAKE RS600 rheometer, the sample was heated and the sample was heated to keep the rheometer rotor sheared at a rate of 170 s -1 . The temperature change was continuously monitored until the temperature rose to the test temperature, and the final viscosity retention was observed after 1 hour of shearing. The results are shown in Figure 1.
  • Figure 1 shows, the whole suspension embodiment 26 of the embodiment of the fracturing fluid at 130 °C, 170s -1 at a shear viscosity remained after 1 hour at 60mPa ⁇ s or more, indicating that the full suspension of the fracturing fluid has good temperature resistance Shearability also indicates that the fracturing fluid has good sand carrying properties.
  • the key to the fracturing fluid is to carry the proppant from the wellbore through the hole to the specified position of the crack front. Therefore, the ability of the fracturing fluid to carry the proppant is a basic requirement.
  • the static suspension performance test of the fully suspended fracturing fluid of Example 26, the polymer fracturing fluid of Comparative Example 1, and the silicone fracturing fluid of Comparative Example 2 were carried out at 90 ° C and a sand ratio of 20%. The test results are shown in Figure 2.
  • the fully suspended fracturing fluid of Example 26 the polymer fracturing fluid of Comparative Example 1, and the ruthenium of Comparative Example 2 at 25 ° C, 90 ° C, a sand ratio of 20%, and a shear rate of 170 s -1 .
  • the rubber fracturing fluid is tested for dynamic sand carrying performance. The test results are shown in Figure 3, Figure 4, Table 4, and Table 5.
  • Fig. 2 the sand-bearing appearance of the three sets of fracturing fluids which are left to stand for 10s, 60s, 1h, and 24h are divided from left to right. It can be seen from Fig. 2 that under the condition of normal temperature and sand ratio of 20%, the sedimentation rate of the proppant is almost zero after 24 hours, and the sand-carrying performance of the fully suspended fracturing fluid is better.
  • the proppant fracturing fluid and the proppant in the conventional polymer fracturing fluid both settled, and after 1 h, the proppant settled obviously. After 24 h, the proppant almost completely settled.
  • Table 4 shows the fully suspended fracturing fluid of Example 26, the polymer fracturing fluid of Comparative Example 1, and the silicone of Comparative Example 2 at 25 ° C, a sand ratio of 20%, and a shear rate of 170 s -1 .
  • Table 5 shows the full suspension fracturing fluid of Example 26, the polymer fracturing fluid of Comparative Example 1, and the ruthenium of Comparative Example 2 at 90 ° C, a sand ratio of 20%, and a shear rate of 170 s -1 .
  • Example 26 It has been verified by theory and experiment that the full suspension fracturing fluid of Example 26 has good sand carrying properties. During the actual fracturing process, the proppant is always in suspension, which can solve the problem of rapid sedimentation of the proppant, contribute to the increase of oil and gas wells, and reduce the amount of proppant and reduce the cost.

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Abstract

一种交联剂、全悬浮压裂液及其制备方法，涉及油田开采技术领域。一种交联剂，主要由按照重量份计的以下组分制作而成：水溶性高价金属盐6～12份，多元醇8～16份，羧酸或其盐4～10份。一种交联剂的制备方法，包括：使水溶性高价金属盐、多元醇、羧酸或其盐分散于溶剂中得到反应液，使反应液在加热和酸性条件下反应。一种全悬浮压裂液，包括由稠化剂与上述交联剂发生交联反应生成的交联产物。一种全悬浮压裂液的制备方法，包括：使稠化剂与上述交联剂进行交联反应。该全悬浮压裂液具有较佳的耐温耐剪切及携砂能力，能够解决支撑剂快速沉降的问题。在获得相同的裂缝长度或裂缝支撑面积的情况下，可明显减少支撑剂的用量，降低成本。

Description

交联剂、全悬浮压裂液及其制备方法
本申请要求于2017年03月27日提交中国专利局的申请号为CN201710186869.3、名称为“交联剂、全悬浮压裂液及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及油气田开采技术领域，且特别涉及一种交联剂、全悬浮压裂液及其制备方法。
背景技术
压裂是一项改造油层渗流特性的工艺技术，是油气井增产、增注的一项重要工艺措施。储层改造是油气井增产的主要措施之一，压裂液是储层改造中的主要液体。压裂液利用地面高压泵组，以超过地层吸收能力的排量注入井中，在井底附近形成高压。此压力超过井底附近地层应力及岩石的抗张强度后，在地层中形成裂缝。压裂液携带支撑剂注入裂缝中，当压裂液破胶返排后，将支撑剂留在裂缝中，改善油气层的导流能力。
携带支撑剂的能力是压裂液关键性能指标，对压裂增产起着至关重要的作用。该全悬浮压裂液具有较佳的耐温耐剪切性及携砂能力，能够解决支撑剂往裂缝下面沉降的问题，并实现支撑剂在裂缝纵向上铺置更均匀，可有效输送支撑剂到裂缝更远端并获得更长的填砂裂缝长度。良好的支撑剂携带能力将有利于提高支撑剂在裂缝的水平方向和纵向上的铺置效率，在相同的加砂规模下，有效支撑裂缝半长和纵向上的支撑高度大幅度提高；要获得相同的有效裂缝半长或裂缝支撑面积，支撑剂及液体用量大幅度降低，成本也大幅度降低，因此携带支撑剂效果越好的压裂液的增产效果也越好。研究出携砂能力强的压裂液对储层的改造具有重要意义。
发明内容
本发明的目的在于提供一种交联剂，该交联剂可与稠化剂反应制得具有全悬浮功能的压裂液，可应用于油气井压裂。
本发明的另一目的在于提供一种交联剂的制备方法，通过该方法制备的交联剂，具有较优的交联能力。
本发明的另一目的在于提供一种全悬浮压裂液，由稠化剂与上述交联剂制得，该全悬浮压裂液具有较佳的耐温耐剪切能力，能够解决采用常规压裂液支撑剂快速沉降的问题，使用该全悬浮压裂液能实现支撑剂接近于零沉降，获得更好的纵向支撑剖面和裂缝半长，有助于油气井的增产，并且可以减少支撑剂的用量，降低成本。
本发明的另一目的在于提供一种全悬浮压裂液的制备方法，通过该制备方法制得的全悬浮压裂液可实现支撑剂接近于零沉降，具有较佳的携砂性。
本发明解决其技术问题是采用以下技术方案来实现的。
本发明提出一种交联剂，主要由按照重量份计的以下组分制作而成：水溶性高价金属盐6～12份，多元醇8～16份，羧酸或其盐4～10份。
根据本发明的交联剂，主要由按照重量份计的以下组分制作而成：所述水溶性高价金属盐6～10份，所述多元醇10～14份，所述羧酸或其盐4～8份。
根据本发明的交联剂，所述水溶性高价金属盐包括柠檬酸铝、三氯化铝、硫酸铝、四氯化锆、氧氯化锆、硫酸锆、醋酸锆、硝酸锆、碳酸锆、碳酸锆铵中的一种或多种。
根据本发明的交联剂，所述多元醇包括乙二醇、聚乙二醇、丙三醇、丙二醇、1,4-丁二醇、甘露醇、三甘醇、木糖醇，三乙醇胺中的一种或多种。
根据本发明的交联剂，所述羧酸包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、酒石酸、葡萄糖酸中的一种或多种。
根据本发明的交联剂，羧酸盐包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、葡萄糖酸的钠盐或钾盐以及酒石酸钠中的一种或多种。
根据本发明的交联剂，所述交联剂还包括无机盐3～15份，所述无机盐包括钠盐、钾盐、镁盐、钙盐中的一种或多种。
本发明还提出一种交联剂的制备方法，包括如下步骤：使水溶性高价金属盐、多元醇、羧酸或其盐分散于溶剂中得到反应液，使反应液在加热和酸性条件下反应。
根据本发明的交联剂的制备方法，所述反应液在加热和酸性条件下反应的方法包括以下步骤：调节所述反应液的pH值至4～7，再加热进行反应。
根据本发明的交联剂的制备方法，采用pH调节剂调整所述反应液的pH值，且所述pH调节剂包括氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠中的一种或多种。
根据本发明的交联剂的制备方法，所述反应液在pH值为4～7的条件下，加热反应的反应温度为40～90℃。
根据本发明的交联剂的制备方法，所述反应液在pH值为4～7、反应温度为40～90℃的条件下，加热反应的反应时间为3～8h。
根据本发明的交联剂的制备方法，调节所述反应液的pH值并加热进行反应后，再加入无机盐，继续反应。
根据本发明的交联剂的制备方法，加入所述无机盐后，继续反应的时间为20～40min。
根据本发明的交联剂的制备方法，所述反应液在加热反应的步骤中，对所述反应液在50～100r/min搅拌速率的条件下进行搅拌。
本发明还提出一种全悬浮压裂液，包括由稠化剂与上述交联剂发生交联反应生成具有空间网络结构的交联产物。
根据本发明的全悬浮压裂液，所述稠化剂包括聚丙烯酰胺类聚合物。
根据本发明的全悬浮压裂液，所述聚丙烯酰胺类聚合物的分子链中引入疏水单体。
根据本发明的全悬浮压裂液，所述交联剂中络合有能与所述聚丙烯酰胺类聚合物形成交联反应的金属离子。
根据本发明的全悬浮压裂液，所述聚丙烯酰胺类聚合物的分子量大于或等于500万。
根据本发明的全悬浮压裂液，所述全悬浮压裂液是以水为分散剂的分散体系。
根据本发明的全悬浮压裂液，所述全悬浮压裂液还包括添加剂。
根据本发明的全悬浮压裂液，所述添加剂包括防膨剂、助排剂、粘度保持剂中的至少一种。
根据本发明的全悬浮压裂液，所述粘度保持剂包括非氧化性杀菌剂、还原剂中的至少一种。
根据本发明的全悬浮压裂液，所述非氧化性杀菌剂包括戊二醛、十二烷基三甲基苄基氯化铵、异噻唑啉酮、苯并异噻唑啉酮中的一种或多种。
根据本发明的全悬浮压裂液，所述还原剂包括硫脲、硫代硫酸钠、亚硫酸钠、亚硫酸氢钠、碘化钾中的一种或多种。
根据本发明的全悬浮压裂液，主要由按质量百分数计的以下组分制成：0.2～0.5％的所述稠化剂、0.3～0.8％的所述交联剂、0.05～1.3％的所述添加剂和余量的水。
根据本发明的全悬浮压裂液，所述防膨剂在所述全悬浮压裂液中的质量百分数为0.1～0.5％，所述助排剂在所述全悬浮压裂液中的质量百分数为0.1～0.5％，所述粘度保持剂在所述全悬浮压裂液中的质量百分数为0.05～0.3％。
根据本发明的全悬浮压裂液，支撑剂在所述全悬浮压裂液中的沉降速度小于2mm/h。
本发明还提出一种全悬浮压裂液的制备方法，包括：使稠化剂与上述交联剂进行交联反应。
根据本发明的全悬浮压裂液的制备方法，所述稠化剂包括聚丙烯酰胺类聚合物。
根据本发明的全悬浮压裂液的制备方法，使所述稠化剂与所述交联剂发生交联反应之前，将所述稠化剂与添加剂混合。
本发明实施例的交联剂、全悬浮压裂液及其制备方法的有益效果是：采用水溶性高价金属盐、多元醇、羧酸或其盐反应制得具有良好交联性的交联剂。该交联剂与聚丙烯酰胺类稠化剂交联形成致密的空间网络结构，使制得的全悬浮压裂液具有良好的耐温性及优越的携砂性，一方面可应用于高温地层中，另一方面使其支撑剂的沉降速度接近于零，在输送过程中保持全悬浮状态，能够有效解决支撑剂快速沉降的问题，减少支撑剂的用量，降低成本，带来很好的经济效益。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本发明实施例26的全悬浮压裂液的流变性能测试图；
图2为本发明实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液的静态携砂性能对比图；
图3为本发明实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液在25℃条件下的动态携砂性能对比图；
图4为本发明实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液在90℃条件下的动态携砂性能对比图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明实施例的交联剂、全悬浮压裂液及其制备方法进行具体说明。
本发明实施例提供的一种交联剂，主要由按照重量份计的以下组分制作而成：水溶性高价金属盐6～12份，多元醇8～16份，羧酸或其盐4～10份。
进一步地，在本发明较佳实施例中，水溶性高价金属盐6～10份，多元醇10～14份，羧酸或其盐4～8份。
水溶性高价金属盐是阳离子为重金属的盐，如铜、铅、锌、铁、钴、镍等。金属盐作为交联剂组分，其金属离子在水中电离、水合后形成水合络离子，可与稠化剂交联。
进一步地，在本发明较佳实施例中，水溶性高价金属盐包括柠檬酸铝、三氯化铝、硫酸铝、四氯化锆、氧氯化锆、硫酸锆、醋酸锆、硝酸锆、碳酸锆、碳酸锆铵中的一种或多种。
进一步地，在本发明较佳实施例中，多元醇包括乙二醇、聚乙二醇、丙三醇、丙二醇、1,4-丁二醇、甘露醇、三甘醇、木糖醇，三乙醇胺中的一种或多种。
进一步地，在本发明较佳实施例中，羧酸包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、酒石酸、葡萄糖酸中的一种或多种。
进一步地，在本发明较佳实施例中，羧酸盐包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、葡萄糖酸的钠盐或钾盐以及酒石酸钠中的一种或多种。
进一步地，在本发明较佳实施例中，交联剂还包括无机盐，无机盐包括钠盐、钾盐、镁盐、钙盐中的一种或多种。在本发明中，无机盐可选用氯化钠、氯化钾、硫酸镁等。
本发明还提供了上述交联剂的制备方法，包括：
在本发明的实施例中，采用水作为反应溶剂；为了使反应物均匀、充分地溶解在水中，在搅拌速率为50～150r/min的条件下，将水溶性高价金属盐、多元醇缓慢的依次加入水中。具体地，缓慢添加水溶性高价金属盐、多元醇的速率为2～4kg/min，较优的，添加水溶性高价金属盐、多元醇的速率为3kg/min。
添加完毕后，进行充分搅拌使反应物完全溶解。具体地，其搅拌时间为10～20min，较优的，搅拌时间为15min。
待完全溶解后，继续缓慢加入羧酸或其盐，保证混合均匀。具体地，添加羧酸或其盐的速率为3～5kg/min，较优的，添加羧酸或其盐的速率为4kg/min。
由于不同的金属离子与配体的反应的pH值不同，故需要调节反应液的pH值使其适于交联剂的生成，并使交联剂具有较好的交联性。具体的，继续搅拌混合溶液待混合均匀后，再缓慢加入pH调节剂，使反应液为酸性，较优的，反应液的pH值为4～7，加热进行反应后，再加入无机盐进行反应。
进一步地，在本发明较佳实施例中，pH调节剂包括氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠中的一种或多种。
调节好反应液的pH值后，对反应液进行加热，达到反应所需的温度进行第一次反应，反应温度为40～90℃，反应时间为3～8h。为了增强交联剂的交联性能，较优的，反应3～8h后再加入无机盐，进行第二次反应，反应时间为20～40min。
在反应的过程中，搅拌有助于交联剂的生成，具体地，加热反应液的同时，在搅拌速率为50～100r/min的条件下进行搅拌，较优的，搅拌速率为75r/min。反应结束后，所得产物即为交联剂。
在该制备方法中，反应物发生配位络合反应，制得可产生多羟桥结构的交联剂。在本发明中，交联剂为有机锆。有机锆作为交联剂具有明显的缓交联特征，有利于压裂液黏度时效性控制，获得较高的裂缝长度，提高压裂效果。
本发明实施例还提供了一种全悬浮压裂液，包括由稠化剂与上述交联剂发生交联反应生成具有空间网络的交联产物。
在本发明中，稠化剂为高分子聚合物。稠化剂与交联剂进行交联时，稠化剂具有交联点，交联点上的孤电子对可与原子空轨道配位，形成分子间和分子内的络合键，进而形成空间网络结构。
进一步地，在本发明较佳实施例中，稠化剂包括聚丙烯酰胺类聚合物。
具体地，聚丙烯酰胺类聚合物为水溶性高分子聚合物。在低浓度下，聚丙烯酰胺溶液可视为网状结构，链间物理缠结和氢键共同形成网状结点，当聚合物达到一定浓度后，分子链间相互作用加强，流体力学体积增大，表现出较高的粘度，故将其作为稠化剂。
进一步地，在本发明较佳实施例中，聚丙烯酰胺类聚合物的分子链中引入疏水单体。
聚丙烯酰胺类聚合物中之所以引入疏水单体是因为：在水溶液中，聚合物的疏水基团由于疏水作用而发生聚集，使大分子链内和分子间缔合。当聚合物浓度高于某一临界浓度后，大分子链通过疏水缔合作用聚集，形成以分子间缔合为主的超分子结构—动态物理交联网络，流体力学体积增大，溶液黏度大幅度升高。
进一步地，在本发明较佳实施例中，交联剂中络合有可与聚丙烯酰胺类聚合物形成交联反应的金属离子。
具体地，在本发明的实施例中，制得的交联剂在溶液中发生水合、水解，生成多核羟桥络离子，与聚丙烯酰胺发生交联，进一步增强空间网络结构，形成致密的网络结构。
稠化剂若具有较大的分子量，大分子链聚集形成网络结构，流体力学体积增大，溶液黏度大幅度升高。进一步地，在本发明较佳实施例中，聚丙烯酰胺类聚合物的分子量大于或等于500万。
目前，水基压裂液是压裂应用的主要类型。进一步地，在本发明较佳实施例中，全悬浮压裂液是以水为分散剂的分散体系。
压裂液在实际应用中，根据不同的地层添加不同的添加剂，在压裂液中加入添加剂可实现其他技术要求，如提高压裂液的防止粘土水化膨胀能力、增加破胶后返排液的排出能力等。进一步地，在本发明较佳实施例中，全悬浮压裂液还包括添加剂。较优的，添加剂包括防膨剂、助排剂、粘度保持剂中的至少一种。
粘土矿物一般表现为电负性，极易水化膨胀，防膨剂可中和粘土表面的负电性，从而阻止粘土的膨胀。较优的，在本发明实施例中，防膨剂可选用氯化钾或其他试剂。
助排剂可以降低压裂液的表面张力或油水界面张力，降低压裂液返排时遇到的毛管阻力。使用助排剂可增大压裂液返排率，缩短排液时间。较优的，在本发明实施例中，助排剂为碳氢类表面活性剂，在本发明其他实施例中，助排剂可以为氟碳类表面活性剂。
粘度保持剂用于防止压裂液粘度降低，使压裂液保持粘度，具有较好的携砂性。较优的，在本发明实施例中，粘度保持剂为非氧化性杀菌剂、还原剂中的至少一种。粘度保持剂可以为硫脲、硫代硫酸钠、亚硫酸钠、亚硫酸氢钠、碘化钾等还原性物质，抑制聚合物的水解和被氧化。特别是在铁和亚铁离子存在的情况下，更需要添加进去，以维持聚合物溶液的性能。粘度保持剂也可以是戊二醛、十二烷基三甲基苄基氯化铵、异噻唑啉酮、苯并异噻唑啉酮等非氧化性杀菌剂，非氧化性杀菌剂预防聚合物水溶液的细菌繁殖引起的粘度下降和性质改变。
进一步地，在本发明较佳实施例中，全悬浮压裂液主要由按质量百分数计的以下组分制成：0.2～0.5％的稠化剂、0.3～0.8％的交联剂、0.05～1％的添加剂和余量的水。
进一步地，在本发明较佳实施例中，防膨剂在全悬浮压裂液中的质量百分数为0.1～0.5％，助排剂在全悬浮压裂液中的质量百分数为0.1～0.5％，粘度保持剂在全悬浮压裂液中的质量百分数为0.05～0.3％。
进一步地，本发明全悬浮压裂液，在施工时可通过添加过硫酸铵作为破胶剂，以本发明较佳实施例为例，在90摄氏度下，过硫酸铵用量在100ppm时，可在2小时控制破胶液粘度小于5mPa·s。
携砂性是评价压裂液性能好坏的重要指标之一。进一步地，在本发明较佳实施例中，支撑剂在全悬浮压裂液中的沉降速度小于2mm/h。较优的，测试压裂液携砂性时，砂比可以为3％～50％，支撑剂可以选用石英砂、陶粒、树脂覆膜砂，支撑剂的粒径可以为5～10目、10～20目、20～40目、30～50目、40～70目等。
本发明还提供了上述全悬浮压裂液的制备方法，包括：
在搅拌的条件下，将稠化剂溶于水中，加料完成后再继续搅拌。较优的，搅拌时间为10～20min；
在搅拌的条件下，加入添加剂；
为了使交联反应充分完全，增加网络结构的紧密程度，在持续搅拌的条件下加入交联剂，交联反应完成即得全悬浮压裂液。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1
本实施例提供的交联剂主要由按照重量份计的以下组分制作而成：
水溶性高价金属盐：氧氯化锆5份；
多元醇：甘露醇8份；
羧酸或其盐：柠檬酸钠4份；
pH调节剂：碳酸钠1份；
无机盐：氯化钾3份；
溶剂：水80份。
交联剂的制备方法包括：
将氧氯化锆5份、甘露醇8份依次加入70份水中，继续加入柠檬酸钠4份，再缓慢加入溶有1份碳酸钠的10份水中调整反应液的pH值，第一次反应在反应温度为40℃的条件下反应3h，再加入氯化钾3份，进行第二次反应，反应时间为30min，反应产物即为交联剂。
实施例2～实施例13的交联剂的制备方法与实施例1相同，具体的组分及反应参数如下表：
表1交联剂的反应组分及反应参数表
Figure PCTCN2017081240-appb-000001
Figure PCTCN2017081240-appb-000002
在表1中，混合盐为柠檬酸铝、氧氯化锆、三氯化铝的混合物，摩尔质量比为1:1:1。混合醇为丙三醇、甘露醇、乙二醇的混合物，摩尔质量比为1:1:1。混合物为乙酸、羟基乙酸、乳酸钠的混合物，摩尔质量比为1:1:1。混合无机盐为氯化钠、氯化钾、氯化钙的混合物，摩尔质量比为1:1:1。
实施例14
本实施例提供的全悬浮压裂液主要由按质量百分数计的以下组分制成：
稠化剂：0.2％的改性聚丙烯酰胺；
交联剂：0.3％的实施例1的交联剂；
防膨剂：1％的氯化钾；
助排剂：0.1％的碳氢类表面活性剂；
粘度保持剂：0.05％的硫脲；
余量的水。
全悬浮压裂液的制备方法包括：
在搅拌的条件下，将0.2wt％的改性聚丙烯酰胺均匀溶于水中，加料完成后再继续搅拌10min，使其充分溶解；在搅拌的条件下，加入1wt％的氯化钾、0.1wt％的碳氢类表面活性剂、0.05wt％的硫脲，混合均匀后在持续搅拌的条件下加入0.3wt％的交联剂，交联反应完成即得全悬浮压裂液。
实施例15～实施例26的全悬浮压裂液的制备工艺流程、所采用的稠化剂、防膨剂、助排剂以及粘度保持剂均与实施例14的相同，具体的反应组分含量及反应参数如下表：
表2全悬浮压裂液反应组分及反应参数表
Figure PCTCN2017081240-appb-000003
对比例1
本对比例提供的聚合物压裂液由以下制备方法制备而成，其包括：
将0.5wt％的聚丙烯酰胺与0.3wt％的氧氯化锆均匀溶于水中，搅拌均匀得到聚合物压裂液。
对比例2
本对比例提供的胍胶压裂液由以下制备方法制备而成，其包括：
将0.4wt％的羟丙基胍胶加入到清水中搅拌30分钟，将0.15wt％碳酸钠加入其中并继续搅拌10分钟得到均匀粘稠状液体，将1wt％的氯化钾、0.3wt％的戊二醛、0.4wt％的交联剂溶于水溶液中搅拌均匀，得到水基胍胶压裂液。
试验例1
对实施例14～26制得的全悬浮压裂液、对比例1制得的聚合物压裂液、对比例2制得的胍胶压裂液进行流变性能测试，测试在130℃、170s-1剪切速率下的粘度，结果如下：
表3粘度对比表
  粘度(mPa·s)
实施例14 32
实施例15 31
实施例16 43
实施例17 36
实施例18 35
实施例19 41
实施例20 56
实施例21 30
实施例22 49
实施例23 54
实施例24 33
实施例25 40
实施例26 60
对比例1 36
对比例2 53
由表3可知，实施例14～26制得的全悬浮压裂液、对比例1制得的聚合物压裂液、对比例2制得的胍胶压裂液中，实施例26的全悬浮压裂液具有较高的粘度。实施例26的全悬浮压裂液以改性的聚丙烯酰胺为稠化剂与实施例13的交联剂(主要成分为有机锆)发生交联，有机锆在溶液中发生水合、水解和羟桥作用形成多核 羟桥络离子，与聚丙烯酰胺发生交联反应，增强空间网络结构的强度，使其制得的全悬浮压裂液具有较好的粘度。
试验例2
对实施例26的全悬浮压裂液进行流变性能测试，测试其耐温耐剪切性能。使用HAAKE RS600型流变仪，样品装填好后对样品进行加热，保持流变仪转子以170s-1的速率对压裂液进行剪切。至温度上升至测试温度条件下，继续监测粘度变化情况，剪切1小时以后观察最终粘度保持情况。结果见图1。
由图1可知，实施例26的全悬浮压裂液在130℃、170s-1下剪切1小时后粘度仍保持在60mPa·s以上，说明该全悬浮压裂液具有较好的耐温耐剪切性，也表明该压裂液具有良好的携砂性能。
试验例3
在实际施工中，压裂液的关键是将支撑剂由井筒经孔眼携带到裂缝前沿指定位置，因此压裂液携带支撑剂能力是基本要求。在90℃、砂比为20％的条件下，对实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液进行静态携砂性能测试。测试结果见图2。在25℃、90℃、砂比为20％、剪切速率为170s-1的条件下，对实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液进行动态携砂性能测试。测试结果见图3、图4、表4、表5。
图2中，由左至右分为别静置10s、60s、1h、24h的三组压裂液的携砂表观图。由图2可知，在常温、砂比为20％的条件下，经过24h其支撑剂的沉降率几乎为零，全悬浮压裂液的携砂性能较好。而胍胶压裂液与常规聚合物压裂液中的支撑剂均发生沉降，且在1h后，支撑剂沉降明显，24h后，支撑剂几乎全部沉降。
图3为在砂比为20％、剪切速率为170s-1的条件下，对实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液进行动态携砂性能测试。图4为在90℃、砂比为20％、剪切速率为170s-1的条件下，对实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液进行动态携砂性能测试。由图3、图4可知，全悬浮压裂液的携砂性能很好，在25℃的条件下，经过动态剪切1小时其支撑剂的沉降率几乎为零，在90℃的条件下，经过动态剪切1小时其 支撑剂几乎不沉降至继续剪切到2小时其支撑剂才有略微下沉。而胍胶压裂液与常规聚合物压裂液中的支撑剂在动态剪切下迅速沉降，在30s后，支撑剂全部沉降。
表4为在25℃、砂比为20％、剪切速率为170s-1的条件下，实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液剪切1h后支撑剂的沉降速率。
表4 25℃时支撑剂沉降速率
压裂液类型 沉降速度(mm/h)
全悬浮压裂液 0
聚合物压裂液 90
胍胶压裂液 90
表5为在90℃、砂比为20％、剪切速率为170s-1的条件下，对实施例26的全悬浮压裂液、对比例1的聚合物压裂液、对比例2的胍胶压裂液剪切1h后支撑剂的沉降速度。
表5 90℃时支撑剂沉降速率
压裂液类型 沉降速度(mm/h)
全悬浮压裂液 0
聚合物压裂液 90
胍胶压裂液 90
由表4、表5可知，实施例26的全悬浮压裂液在不同的条件下，支撑剂的沉降速度均为0mm/h，而对比例1的聚合物压裂液、对比例2的胍胶压裂液的支撑剂的沉降速度均较大，说明实施例26的全悬浮压裂液具有良好的携砂性。
经理论及实验验证，实施例26的全悬浮压裂液具有良好的携砂性。在实际压裂过程中，支撑剂始终保持悬浮状态，能够解决支撑剂快速沉降的问题，有助于油气井的增产，并且可以减少支撑剂的用量，降低成本。
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。

Claims (32)

  1. 一种交联剂，其特征在于，主要由按照重量份计的以下组分制作而成：水溶性高价金属盐6～12份，多元醇8～16份，羧酸或其盐4～10份。
  2. 根据权利要求1所述的交联剂，其特征在于，主要由按照重量份计的以下组分制作而成：所述水溶性高价金属盐6～10份，所述多元醇10～14份，所述羧酸或其盐4～8份。
  3. 根据权利要求1所述的交联剂，其特征在于，所述水溶性高价金属盐包括柠檬酸铝、三氯化铝、硫酸铝、四氯化锆、氧氯化锆、硫酸锆、醋酸锆、硝酸锆、碳酸锆、碳酸锆铵中的一种或多种。
  4. 根据权利要求1所述的交联剂，其特征在于，所述多元醇包括乙二醇、聚乙二醇、丙三醇、丙二醇、1,4-丁二醇、甘露醇、三甘醇、木糖醇，三乙醇胺中的一种或多种。
  5. 根据权利要求1所述的交联剂，其特征在于，所述羧酸包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、酒石酸、葡萄糖酸中的一种或多种。
  6. 根据权利要求1所述的交联剂，其特征在于，羧酸盐包括甲酸、乙酸、羟基乙酸、乳酸、柠檬酸、葡萄糖酸的钠盐或钾盐以及酒石酸钠中的一种或多种。
  7. 根据权利要求1所述的交联剂，其特征在于，所述交联剂还包括无机盐3～15份，所述无机盐包括钠盐、钾盐、镁盐、钙盐中的一种或多种。
  8. 一种如权利要求1所述的交联剂的制备方法，其特征在于，包括以下步骤：使所述水溶性高价金属盐、所述多元醇、所述羧酸或其盐分散于溶剂中得到反应液，使所述反应液在加热和酸性条件下反应。
  9. 根据权利要求8所述的交联剂的制备方法，其特征在于，所述反应液在加热和酸性条件下反应的方法包括以下步骤：调节所述反应液的pH值至4～7，再加热进行反应。
  10. 根据权利要求9所述的交联剂的制备方法，其特征在于，采用pH调节剂调整所述反应液的pH值，且所述pH调节剂包括氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠中的一种或多种。
  11. 根据权利要求9所述的交联剂的制备方法，其特征在于，所述反应液在pH值为4～7的条件下，加热反应的反应温度为40～90℃。
  12. 根据权利要求9所述的交联剂的制备方法，其特征在于，所述反应液在pH值为4～7、反应温度为40～90℃的条件下，加热反应的反应时间为3～8h。
  13. 根据权利要求9所述的交联剂的制备方法，其特征在于，调节所述反应液的pH值并加热进行反应后，再加入无机盐，继续反应。
  14. 根据权利要求13所述的交联剂的制备方法，其特征在于，加入所述无机盐后，继续反应的时间为20～40min。
  15. 根据权利要求8所述的交联剂的制备方法，其特征在于，所述反应液在加热反应的步骤中，对所述反应液在50～100r/min搅拌速率的条件下进行搅拌。
  16. 一种全悬浮压裂液，其特征在于，包括由稠化剂与如权利要求1至7中任一项所述的交联剂发生交联反应生成具有空间网络结构的交联产物。
  17. 根据权利要求16所述的全悬浮压裂液，其特征在于，所述稠化剂包括聚丙烯酰胺类聚合物。
  18. 根据权利要求17所述的全悬浮压裂液，其特征在于，所述聚丙烯酰胺类聚合物的分子链中引入疏水单体。
  19. 根据权利要求17所述的全悬浮压裂液，其特征在于，所述交联剂中络合有能与所述聚丙烯酰胺类聚合物形成交联反应的金属离子。
  20. 根据权利要求17所述的全悬浮压裂液，其特征在于，所述聚丙烯酰胺类聚合物的分子量大于或等于500万。
  21. 根据权利要求16所述的全悬浮压裂液，其特征在于，所述全悬浮压裂液是以水为分散剂的分散体系。
  22. 根据权利要求16所述的全悬浮压裂液，其特征在于，所述全悬浮压裂液还包括添加剂。
  23. 根据权利要求22所述的全悬浮压裂液，其特征在于，所述添加剂包括防膨剂、助排剂、粘度保持剂中的至少一种。
  24. 根据权利要求23所述的全悬浮压裂液，其特征在于，所述粘度保持剂包括非氧化性杀菌剂、还原剂中的至少一种。
  25. 根据权利要求24所述的全悬浮压裂液，其特征在于，所述非氧化性杀菌剂包括戊二醛、十二烷基三甲基苄基氯化铵、异噻唑啉酮、苯并异噻唑啉酮中的一种或多种。
  26. 根据权利要求24所述的全悬浮压裂液，其特征在于，所述还原剂包括硫脲、硫代硫酸钠、亚硫酸钠、亚硫酸氢钠、碘化钾中的一种或多种。
  27. 根据权利要求22所述的全悬浮压裂液，其特征在于，主要由按质量百分数计的以下组分制成：0.2～0.5％的所述稠化剂、0.3～0.8％的所述交联剂、0.05～1.3％的所述添加剂和余量的水。
  28. 根据权利要求23所述的全悬浮压裂液，其特征在于，所述防膨剂在所述全悬浮压裂液中的质量百分数为0.1～0.5％，所述助排剂在所述全悬浮压裂液中的质量百分数为0.1～0.5％，所述粘度保持剂在所述全悬浮压裂液中的质量百分数为0.05～0.3％。
  29. 根据权利要求16所述的全悬浮压裂液，其特征在于，支撑剂在所述全悬浮压裂液中的沉降速度小于2mm/h。
  30. 一种全悬浮压裂液的制备方法，其特征在于，包括：使稠化剂与如权利要求1至7中任一项所述的交联剂进行交联反应。
  31. 根据权利要求30所述的全悬浮压裂液的制备方法，其特征在于，所述稠化剂包括聚丙烯酰胺类聚合物。
  32. 根据权利要求30所述的全悬浮压裂液的制备方法，其特征在于，使所述稠化剂与所述交联剂发生交联反应之前，将所述稠化剂与添加剂混合。
PCT/CN2017/081240 2017-03-27 2017-04-20 交联剂、全悬浮压裂液及其制备方法 WO2018176532A1 (zh)

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