CN104371699A - Organic aluminum-zirconium crosslinking agent and preparation method thereof, and low-molecular polymer fracturing fluid - Google Patents

Organic aluminum-zirconium crosslinking agent and preparation method thereof, and low-molecular polymer fracturing fluid Download PDF

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CN104371699A
CN104371699A CN201410642957.6A CN201410642957A CN104371699A CN 104371699 A CN104371699 A CN 104371699A CN 201410642957 A CN201410642957 A CN 201410642957A CN 104371699 A CN104371699 A CN 104371699A
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parts
zirconium
low
weight
molecular
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常李博
蒋尔梁
彭元东
贾跃立
刘欣
孙彬峰
李梦楠
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China Petroleum and Chemical Corp
Petroleum Engineering Technology Research Institute of Sinopec Henan Oilfield Branch Co
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China Petroleum and Chemical Corp
Petroleum Engineering Technology Research Institute of Sinopec Henan Oilfield Branch Co
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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
    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents

Abstract

The invention discloses an organic aluminum-zirconium crosslinking agent and a preparation method thereof, and a low-molecular polymer fracturing fluid. The crosslinking agent is prepared by reacting the following raw materials in parts by weight: 15-25 parts of zirconium salt, 15-25 parts of aluminum salt, 150-250 parts of polyalcohol, 75-85 parts of organic acid, 15-25 parts of gluconate and 55-65 parts of water. The organic aluminum-zirconium crosslinking agent has excellent high temperature resistance, and has favorable crosslinking effect under the conditions of high temperature and high salinity. The organic aluminum-zirconium crosslinking agent is stable under the condition of low pH value, can implement acid crosslinking, and ensures the normal proceeding of the acid fracturing. The organic aluminum-zirconium crosslinking agent has favorable compatibility with polymers and high crosslinking capacity; and the fracturing fluid formed by compounding the organic aluminum-zirconium crosslinking agent with polymers has the advantages of stable gel, excellent solid carrying capacity, excellent viscosity breaking performance and excellent shearing resistance under high-temperature conditions. The organic aluminum-zirconium crosslinking agent has the characteristics of high solubility, no pollution and low damage degree to the reservoir, and has wide application prospects.

Description

A kind of organoaluminum zirconium crosslink agent, preparation method and low-molecular(weight)polymer fracturing liquid
Technical field
The invention belongs to oil field chemical agent technical field, be specifically related to a kind of organoaluminum zirconium crosslink agent, also relate to a kind of preparation method of organoaluminum zirconium crosslink agent simultaneously and use the low-molecular(weight)polymer fracturing liquid of this linking agent.
Background technology
Waterfrac treatment is an important technique measure of well production increment, intensified injection of wells.The object of pressure break forms the crack with certain size and flow conductivity in the earth formation, and its success or not and of the fracturing fluid performance used have much relations.Waterfrac treatment has certain requirement for of the fracturing fluid performance, as aspects such as tackifying, suspension, leak-off, friction loss, stability, formation damages.At present, be widely used in fracturing fluid system is still aqueous fracturing fluid (accounting for 65%).And in aqueous fracturing fluid, boron crosslinked fracturing fluid accounts for 40%, titanium, zirconium crosslinked fracturing fluid account for 10%, and uncrosslinked linear glue accounts for 15%.But conventional aqueous fracturing fluid needs the crosslinked environment of alkalescence and there is the more problem of residue, more serious to the injury of hyposmosis, the quick reservoir of alkali.At present, the fracturing fluid system that oil field uses is mostly HPG, borate crosslinker and other additives and forms.HPG be melon glue through hydroxypropylation, although its residue content reduces many compared with melon glue, but still inevitable containing many water-insolubles, the injury of its formation is comparatively large, cannot meet the requirement of high temperature and deep layer fracturing transformation; And due to melon glue price increase in recent years, relative of the fracturing fluid cost is also higher.
Polymer fracturing fluid starts to come into one's own in recent years, and polymers soln can obtain better visco-elasticity under linking agent effect, can meet the prop-carrying capacity needed for fracturing reform preferably.Wherein, the performance of linking agent directly determines the quality of fracturing effect in oil recovery process.But; common linking agent is as undesirable in the cross-linking effect of organic borate cross-linker to synthetic polymer, and along with the exploitation of hydrocarbon-bearing pool long-term injecting water, most of stratum is now alkali sensitivity stratum; along with the protection of formation is more and more important, the quick problem of stratum alkali that borate crosslinker brings is also very important.Other also have use as independent organoaluminum linking agent, but it is unstable in low ph value, and be easily hydrolyzed under high temperature and high salinity, cause gel instability problem, use range is very limited.
Summary of the invention
The object of this invention is to provide a kind of high temperature resistant, acid organoaluminum zirconium crosslink agent that cross-linking properties is good.
Second object of the present invention is to provide a kind of preparation method of organoaluminum zirconium crosslink agent.
3rd object of the present invention is to provide a kind of low-molecular(weight)polymer fracturing liquid using above-mentioned linking agent.
In order to realize above object, the technical solution adopted in the present invention is: a kind of organoaluminum zirconium crosslink agent, is obtained by the raw material reaction of following parts by weight: zirconates 15 ~ 25 parts, aluminium salt 15 ~ 25 parts, polyvalent alcohol 150 ~ 250 parts, organic acid 75 ~ 85 parts, gluconate 15 ~ 25 parts, 55 ~ 65 parts, water.
Described zirconates is any one or two kinds in zirconium oxychloride, tri-chlorination zirconium; Described aluminium salt is any one or two kinds in aluminum chloride, Tai-Ace S 150.
Described polyvalent alcohol is any one or combination in polymeric alcohol, glycol ether.
Described organic acid is any one or two kinds in lactic acid, acetic acid.
Described gluconate is any one or two kinds in Sunmorl N 60S, Potassium Gluconate.
Described reaction is back flow reaction, and temperature of reaction is 45 ~ 55 DEG C, and the reaction times is 4 ~ 6h.
A preparation method for above-mentioned organoaluminum zirconium crosslink agent, comprises the following steps:
1) polyvalent alcohol getting formula ratio is added to the water, and is warming up to 45 ~ 55 DEG C, obtains mixture after mixing;
2) to step 1) add aluminium salt, the zirconates of formula ratio in gained mixture, after stirring and dissolving, then add gluconate and organic acid successively, at 45 ~ 55 DEG C, back flow reaction 4 ~ 6h under agitation condition, obtain described organoaluminum zirconium crosslink agent.
Use a low-molecular(weight)polymer fracturing liquid for above-mentioned organoaluminum zirconium crosslink agent, comprise the component of following volume parts: the low-molecular(weight)polymer aqueous solution 97 ~ 98.5 parts, organoaluminum zirconium crosslink agent 0.3 ~ 0.8 part, cleanup additive 0.5 ~ 1 part, clay stabilizer 0.5 ~ 2 part.
In the described low-molecular(weight)polymer fracturing liquid aqueous solution, the mass percentage of low-molecular(weight)polymer is 0.5% ~ 1%, and pH value is 5 ~ 6.
Described low-molecular(weight)polymer is polyacrylamide.Molecular weight≤8,000,000 of described polyacrylamide.
The molecular weight of described low-molecular(weight)polymer is 300,000 ~ 1,000,000.
Described cleanup additive is any one or two kinds in DL-8 type cleanup additive, s-203 cleanup additive.
Described clay stabilizer is Repone K.
Described low-molecular(weight)polymer fracturing liquid is prepared by following methods:
Under agitation condition, after cleanup additive, clay stabilizer being mixed, obtain additive solution; Under agitation condition, after being mixed with additive solution by the low-molecular(weight)polymer aqueous solution, then add organoaluminum zirconium crosslink agent, mix, obtain described low-molecular(weight)polymer fracturing liquid.
Organoaluminum zirconium crosslink agent of the present invention, react obtained by zirconates, aluminium salt, polyvalent alcohol, organic acid, gluconate, water, this linking agent has excellent resistance to elevated temperatures, under high temperature, high salinity, have good cross-linking effect; Stablize at the low ph, can acid cross-linked be realized, ensure normally carrying out of acid fracturing; Have good compatibleness with polymkeric substance, crosslinking ability is strong, the fracturing liquid composite with polymkeric substance, and under the high temperature conditions, gel stability, has excellent prop-carrying capacity, broken colloidality energy and resistant to shearing performance; Meanwhile, there is soluble, pollution-free, little to the extent of injury of reservoir feature, have broad application prospects.
The preparation method of organoaluminum zirconium crosslink agent of the present invention reacts obtained after zirconates, aluminium salt, polyvalent alcohol, organic acid, gluconate being mixed with water; Raw material sources are extensive, cheap; Gained linking agent has excellent resistance to elevated temperatures, has good compatibleness with low-molecular(weight)polymer, and under acidic conditions, crosslinking ability is strong, the gel stability of formation, and prop-carrying capacity is strong; This preparation method's technique is simple, and easy to operate, cost is low, is easy to extemporaneous preparation, is applicable to large-scale industrial production.
Low-molecular(weight)polymer fracturing liquid of the present invention, form primarily of the low-molecular(weight)polymer aqueous solution, organoaluminum zirconium crosslink agent, cleanup additive and clay stabilizer, the compatibleness of organoaluminum zirconium crosslink agent and low-molecular(weight)polymer is strong, the gel stability of formation, without precipitation, separation phenomenon; This fracturing liquid has excellent resistance to elevated temperatures, under hot conditions, resistant to shearing ability is strong, mass concentration is that the fracturing liquid that the low-molecular(weight)polymer aqueous solution of 0.8wt% and organoaluminum zirconium crosslink agent are cross-linked to form can be resistance to 150 DEG C, and after shearing 120min, tail is sticky still higher than more than 50mpas; Meanwhile, also have excellent take grittiness can and broken colloidality energy, this system sand settling speed is 0.00015cm/min, takes grittiness energy good; This system 90 DEG C, add 1% ammonium persulphate gel breaker condition under, the broken glue time is 1h, and the viscosity of breaking glue solution is all less than 4.2mPas, and broken colloidality can be excellent; Residue is less, and by showing breaking glue solution matrix permeability of rock core damage experiment, this system reduces core permeability 8.2%, lower to reservoir damage degree, is applicable to applying.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained low-molecular(weight)polymer of the fracturing fluid temperature and shearing sustainability test result schematic diagram;
Fig. 2 is embodiment 2 gained low-molecular(weight)polymer of the fracturing fluid temperature and shearing sustainability test result schematic diagram;
Fig. 3 is embodiment 3 gained low-molecular(weight)polymer of the fracturing fluid temperature and shearing sustainability test result schematic diagram.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
In embodiment, DL-8 type cleanup additive used is purchased from Xinxiang Xuan Tai Industrial Co., Ltd.; S-203 cleanup additive is purchased from Dongying City Sheng Dou Petrotechnik Ltd..
Embodiment 1
The organoaluminum zirconium crosslink agent of the present embodiment is obtained by the raw material reaction of following parts by weight:
The preparation method of the organoaluminum zirconium crosslink agent of the present embodiment, comprises the following steps:
1) getting 180g glycol ether adds in 55g water, is warming up to 45 DEG C, obtains mixture after mixing;
2) under agitation condition, to step 1) add 18g aluminum chloride, 18g tri-chlorination zirconium in gained mixture, stirring and dissolving, after mixing, add 15g Potassium Gluconate and 78g glacial acetic acid under agitation successively, then at 45 DEG C, back flow reaction 4.5h under agitation condition, described organoaluminum zirconium crosslink agent is obtained.
The low-molecular(weight)polymer fracturing liquid of the above-mentioned organoaluminum zirconium crosslink agent of use of the present embodiment, comprises the component of following volume parts:
Wherein, described low-molecular(weight)polymer is polyacrylamide, and molecular weight is 2,800,000; In the described low-molecular(weight)polymer aqueous solution, the mass percentage of low-molecular(weight)polymer is 0.5%, pH is 5 ~ 6.
The low-molecular(weight)polymer fracturing liquid of the present embodiment is prepared by following methods:
Under agitation condition, after cleanup additive, clay stabilizer being mixed, obtain additive solution; Under agitation condition, after being mixed with additive solution by the low-molecular(weight)polymer aqueous solution, then add organoaluminum zirconium crosslink agent, mix, obtain described low-molecular(weight)polymer fracturing liquid.
Adopt the of the fracturing fluid temperature and shearing sustainability of RS600 rheometer test the present embodiment gained low-molecular(weight)polymer, the results are shown in Figure 1.As can be seen from Figure 1, the present embodiment gained low-molecular(weight)polymer fracturing liquid is at 120 DEG C, 170s -1shear 80 minutes, fracturing liquid tail glues for 157.8mpas, shows excellent temperature and shearing sustainability.
Embodiment 2
The organoaluminum zirconium crosslink agent of the present embodiment is obtained by the raw material reaction of following parts by weight:
The preparation method of the organoaluminum zirconium crosslink agent of the present embodiment, comprises the following steps:
1) getting 200g polymeric alcohol adds in 60g water, is warming up to 50 DEG C, obtains mixture after mixing;
2) under agitation condition, to step 1) add 20g aluminum chloride, 20g basic zirconium chloride in gained mixture, stirring and dissolving, after mixing, add 20g Sunmorl N 60S and 80g lactic acid under agitation successively, then at 50 DEG C, back flow reaction 5h under agitation condition, described organoaluminum zirconium crosslink agent is obtained.
The low-molecular(weight)polymer fracturing liquid of the above-mentioned organoaluminum zirconium crosslink agent of use of the present embodiment, comprises the component of following volume parts:
Wherein, described low-molecular(weight)polymer is polyacrylamide, and molecular weight is 4,200,000; In the described low-molecular(weight)polymer aqueous solution, the mass percentage of low-molecular(weight)polymer is 0.6%, pH is 5 ~ 6.
The of the fracturing fluid preparation method of low-molecular(weight)polymer of the present embodiment is with embodiment 1.
Adopt the of the fracturing fluid temperature and shearing sustainability of RS600 rheometer test the present embodiment gained low-molecular(weight)polymer, the results are shown in Figure 2.As can be seen from Figure 2, the present embodiment gained low-molecular(weight)polymer fracturing liquid is at 130 DEG C, 170s -1shear 90 minutes, fracturing liquid tail glues for 58.44mpas, shows excellent temperature and shearing sustainability.
Embodiment 3
The organoaluminum zirconium crosslink agent of the present embodiment is obtained by the raw material reaction of following parts by weight:
The preparation method of the organoaluminum zirconium crosslink agent of the present embodiment, comprises the following steps:
1) getting 220g polymeric alcohol adds in 65g water, is warming up to 55 DEG C, obtains mixture after mixing;
2) under agitation condition, to step 1) add 22g Tai-Ace S 150,22g basic zirconium chloride in gained mixture, stirring and dissolving, after mixing, add 22g Potassium Gluconate and 50g lactic acid, 30g glacial acetic acid under agitation successively, then at 55 DEG C, back flow reaction 5.5h under agitation condition, described organoaluminum zirconium crosslink agent is obtained.
The low-molecular(weight)polymer fracturing liquid of the above-mentioned organoaluminum zirconium crosslink agent of use of the present embodiment, comprises the component of following volume parts:
Wherein, described low-molecular(weight)polymer is polyacrylamide, and molecular weight is 4,500,000; In the described low-molecular(weight)polymer aqueous solution, the mass percentage of low-molecular(weight)polymer is 0.7%, pH is 5 ~ 6.
The of the fracturing fluid preparation method of low-molecular(weight)polymer of the present embodiment is with embodiment 1.
Adopt the of the fracturing fluid temperature and shearing sustainability of RS600 rheometer test the present embodiment gained low-molecular(weight)polymer, the results are shown in Figure 3.As can be seen from Figure 3, the present embodiment gained low-molecular(weight)polymer fracturing liquid is at 150 DEG C, 170s -1shear 120 minutes, fracturing liquid tail glues for 75.07mpas, shows excellent temperature and shearing sustainability.
Embodiment 4
The organoaluminum zirconium crosslink agent of the present embodiment is obtained by the raw material reaction of following parts by weight:
The preparation method of the organoaluminum zirconium crosslink agent of the present embodiment, comprises the following steps:
1) get 100g polymeric alcohol, 145g glycol ether adds in 55g water, be warming up to 55 DEG C after mixing, obtain mixture;
2) under agitation condition, to step 1) add 15g Tai-Ace S 150,15g basic zirconium chloride, 10g tri-chlorination zirconium in gained mixture, stirring and dissolving, after mixing, add 15g Potassium Gluconate and 75g lactic acid under agitation successively, then at 55 DEG C, back flow reaction 4h under agitation condition, described organoaluminum zirconium crosslink agent is obtained.
The low-molecular(weight)polymer fracturing liquid of the above-mentioned organoaluminum zirconium crosslink agent of use of the present embodiment, comprises the component of following volume parts:
Wherein, described low-molecular(weight)polymer is polyacrylamide, and molecular weight is 6,300,000; In the described low-molecular(weight)polymer aqueous solution, the mass percentage of low-molecular(weight)polymer is 0.8%, pH is 5 ~ 6.
The of the fracturing fluid preparation method of low-molecular(weight)polymer of the present embodiment is with embodiment 1.
Adopt the of the fracturing fluid temperature and shearing sustainability of RS600 rheometer test the present embodiment gained low-molecular(weight)polymer.The present embodiment gained low-molecular(weight)polymer fracturing liquid is at 150 DEG C, 170s -1shear 120 minutes, fracturing liquid tail is sticky higher than 50mpas, shows excellent temperature and shearing sustainability.
Embodiment 5
The organoaluminum zirconium crosslink agent of the present embodiment is obtained by the raw material reaction of following parts by weight:
The preparation method of the organoaluminum zirconium crosslink agent of the present embodiment, comprises the following steps:
1) getting 155g glycol ether adds in 65g water, is warming up to 50 DEG C, obtains mixture after mixing;
2) under agitation condition, to step 1) add 10g aluminum chloride, 15g Tai-Ace S 150,15g tri-chlorination zirconium in gained mixture, stirring and dissolving, after mixing, add 20g Potassium Gluconate, 5g Sunmorl N 60S and 85g glacial acetic acid under agitation successively, then at 50 DEG C, back flow reaction 5h under agitation condition, described organoaluminum zirconium crosslink agent is obtained.
The low-molecular(weight)polymer fracturing liquid of the above-mentioned organoaluminum zirconium crosslink agent of use of the present embodiment, comprises the component of following volume parts:
Wherein, described low-molecular(weight)polymer is polyacrylamide, and molecular weight is 6,900,000; In the described low-molecular(weight)polymer aqueous solution, the mass percentage of low-molecular(weight)polymer is 1.0%, pH is 5 ~ 6.
The of the fracturing fluid preparation method of low-molecular(weight)polymer of the present embodiment is with embodiment 1.
Adopt the of the fracturing fluid temperature and shearing sustainability of RS600 rheometer test the present embodiment gained low-molecular(weight)polymer.The present embodiment gained low-molecular(weight)polymer fracturing liquid is at 150 DEG C, 170s -1shear 90 minutes, fracturing liquid tail is sticky higher than 50mpas, shows excellent temperature and shearing sustainability.
Experimental example
This experimental example detects the of the fracturing fluid prop-carrying capacity of embodiment 1-5 gained low-molecular(weight)polymer, broken colloidality energy and formation extent of injury.
Detection method is as follows:
One, sand performance evaluation is taken: evaluate of the fracturing fluid prop-carrying capacity by sand settling speed.Specific experiment method is:
(1) quartz sand (20 ~ 40 order) is crossed 0.500mm and 0.420mm testing sieve successively, get quartz sand (0.420mm ~ 0.500mm) conduct on 0.420mm testing sieve and measure sandstone settling velocity quartz sand used;
(2) 250ml sand-carrying agent is poured in graduated cylinder, being placed in temperature is 30 DEG C ± 1 DEG C water bath with thermostatic control, after constant temperature, with tweezers get one sieve after quartz sand (0.420mm ~ 0.500mm) put into 2cm place under liquid level, unclamp tweezers, make its natural subsidence;
(3) quartz sand uniform settling certain distance L required time t is recorded, replication three times;
(4) sand settling speed is calculated as follows:
v = L t - - - ( 1 ) ;
In formula: ν-sand settling speed, unit is a centimetre per minute (cm/min);
L-sand settling distance, unit is centimetre (cm);
T-sand settling time, unit is point (min).
Two, broken glue performance evaluation: under 90 DEG C of conditions, under adding 1% ammonium persulphate gel breaker condition, detects the viscosity of broken glue time and breaking glue solution.
Three, formation injury performance evaluation: evaluate this fracturing liquid formation extent of injury by breaking glue solution matrix permeability of rock core damage experiment.Concrete operations are:
(1) natural core: washing oil, find time saturated local water or normal saline solution; Synthetic core: only need find time saturated local water or normal saline solution.
(2) core permeability K 1mensuration: salt solution clamp-ons rock core from rock core left end, and the salt solution in displacement rock core space, after pressure, flow speed stability, records rate of permeation.
(3) fracturing liquid filtrate clamp-ons rock core: fracturing liquid filtrate loaded in high pressure vessel, with pressure source pressurization, makes filtrate enter rock core (with to clamp-on salt solution identical with the direction of kerosene) from core holding unit left end.Clamp-on pressure reduction to determine according to core permeability size, be generally 0.5MPa.Clamp-on amount of filtrate to be limited with 1PV or 36min, after having squeezed, close clamper two ends valve, make filtrate stop 2h in rock core, experimental temperature is fracturing liquid Applicable temperature.
(4) brine displacements surveys core permeability K 2: measure the rate of permeation K of rock core by the salt solution after the infringement of fracturing liquid filtrate by the method for (2) 2, require that displacement liquid measure is 5 ~ 15 times of volume of voids.
Core permeability is calculated as follows:
K = Q × μ × L Δp × A * 0.1 - - - ( 2 ) ;
In formula: K-salt solution by the rate of permeation of rock core, μm 2;
Q-salt solution by the volumetric flow rate of rock core, ml/s;
L-rock core axial length, cm;
A-rock core cross-sectional area, cm 2;
μ-brine viscosity, mPas; Get 1mPas;
Δ p-rock core displacement pressure reduction, MPa.
Matrix permeability damaging factor is calculated as follows:
η d = K 1 - K 2 K 1 × 100 - - - ( 3 ) ;
In formula: η d-permeability damage rate, %;
K 1-rock core clamp-ons the matrix permeability before fracturing liquid, and μm 2;
K 2-rock core clamp-ons the matrix permeability after fracturing liquid, and μm 2;
Table 1 low-molecular(weight)polymer fracturing fluid property detected result
Wherein, organoaluminum linking agent is not containing tri-chlorination zirconium, and all the other are with embodiment 1; Organic zirconium crosslinker is not containing aluminum chloride, and all the other are with embodiment 1.
As can be seen from Table 1, to adopting organoaluminum linking agent, the fracturing liquid of organic zirconium crosslinker compares, and adopts the low-molecular(weight)polymer fracturing liquid of embodiment 1-5 gained organoaluminum zirconium crosslink agent taking grittiness energy, broken colloidality energy and to the linking agent being all better than aluminium in core damage rate, zirconium is used alone.Experimental result shows, adopt the low-molecular(weight)polymer fracturing liquid of organoaluminum zirconium crosslink agent of the present invention have excellent take grittiness can and broken colloidality energy, simultaneously little to the injury rate of reservoir, have broad application prospects.

Claims (10)

1. an organoaluminum zirconium crosslink agent, is characterized in that: be obtained by the raw material reaction of following parts by weight: zirconates 15 ~ 25 parts, aluminium salt 15 ~ 25 parts, polyvalent alcohol 150 ~ 250 parts, organic acid 75 ~ 85 parts, gluconate 15 ~ 25 parts, 55 ~ 65 parts, water.
2. organoaluminum zirconium crosslink agent according to claim 1, is characterized in that: described zirconates is any one or two kinds in zirconium oxychloride, tri-chlorination zirconium; Described aluminium salt is any one or two kinds in aluminum chloride, Tai-Ace S 150.
3. organoaluminum zirconium crosslink agent according to claim 1, is characterized in that: described polyvalent alcohol is any one or combination in polymeric alcohol, glycol ether.
4. organoaluminum zirconium crosslink agent according to claim 1, is characterized in that: described organic acid is any one or two kinds in lactic acid, acetic acid.
5. organoaluminum zirconium crosslink agent according to claim 1, is characterized in that: described gluconate is any one or two kinds in Sunmorl N 60S, Potassium Gluconate.
6. a preparation method for organoaluminum zirconium crosslink agent as claimed in claim 1, is characterized in that: comprise the following steps:
1) polyvalent alcohol getting formula ratio is added to the water, and is warming up to 45 ~ 55 DEG C, obtains mixture after mixing;
2) to step 1) add aluminium salt, the zirconates of formula ratio in gained mixture, after stirring and dissolving, then add gluconate and organic acid successively, at 45 ~ 55 DEG C, back flow reaction 4 ~ 6h under agitation condition, obtain described organoaluminum zirconium crosslink agent.
7. use a low-molecular(weight)polymer fracturing liquid for organoaluminum zirconium crosslink agent as claimed in claim 1, it is characterized in that: the component comprising following volume parts: the low-molecular(weight)polymer aqueous solution 97 ~ 98.5 parts, organoaluminum zirconium crosslink agent 0.3 ~ 0.8 part, cleanup additive 0.5 ~ 1 part, clay stabilizer 0.5 ~ 2 part.
8. low-molecular(weight)polymer fracturing liquid according to claim 7, is characterized in that: described low-molecular(weight)polymer is polyacrylamide.
9. low-molecular(weight)polymer fracturing liquid according to claim 7, is characterized in that: described cleanup additive is any one or two kinds in DL-8 type cleanup additive, s-203 cleanup additive.
10. low-molecular(weight)polymer fracturing liquid according to claim 7, is characterized in that: described clay stabilizer is Repone K.
CN201410642957.6A 2014-11-07 2014-11-07 Organic aluminum-zirconium crosslinking agent and preparation method thereof, and low-molecular polymer fracturing fluid Pending CN104371699A (en)

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CN105778883A (en) * 2016-04-21 2016-07-20 成都劳恩普斯科技有限公司 Full-suspension cleaning polymer fracturing fluid and preparation method thereof
CN105860951A (en) * 2016-05-16 2016-08-17 中国石油化工股份有限公司 Acidic polymer fracturing fluid and preparation method thereof
CN106928959A (en) * 2017-03-27 2017-07-07 成都劳恩普斯科技有限公司 Crosslinking agent, full suspension fracturing fluid and preparation method thereof
CN108456513A (en) * 2017-02-20 2018-08-28 中国石油化工股份有限公司 A kind of fracturing fluid organic aluminum crosslinker, preparation method and application
CN109735318A (en) * 2019-01-21 2019-05-10 克拉玛依中科恒信科技有限责任公司 A kind of pressure break enhanced type controllable cross-linking agent and preparation method thereof
CN110437819A (en) * 2019-09-17 2019-11-12 四川洁能锐思石油技术有限公司 A kind of low polymer fracturing fluid and preparation method thereof
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CN114437705A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 Organic crosslinking acid and organic aluminum zirconium crosslinking agent for acid fracturing and preparation method thereof
CN115287054A (en) * 2022-08-23 2022-11-04 洲际海峡能源科技有限公司 Organic aluminum crosslinking agent, preparation method thereof and application thereof in continuous mixed fracturing fluid

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Cited By (13)

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CN104845606A (en) * 2015-05-05 2015-08-19 中国石油天然气股份有限公司 Viscoelastic polymer clean fracturing fluid suitable for wastewater preparation
CN105295885A (en) * 2015-11-06 2016-02-03 中国石油化工股份有限公司 Acid polymer weighted fracture fluid and preparation method thereof
CN105778883A (en) * 2016-04-21 2016-07-20 成都劳恩普斯科技有限公司 Full-suspension cleaning polymer fracturing fluid and preparation method thereof
CN105860951A (en) * 2016-05-16 2016-08-17 中国石油化工股份有限公司 Acidic polymer fracturing fluid and preparation method thereof
CN108456513B (en) * 2017-02-20 2021-09-10 中国石油化工股份有限公司 Organic aluminum crosslinking agent for fracturing fluid, preparation method and application
CN108456513A (en) * 2017-02-20 2018-08-28 中国石油化工股份有限公司 A kind of fracturing fluid organic aluminum crosslinker, preparation method and application
CN106928959B (en) * 2017-03-27 2018-10-26 成都劳恩普斯科技有限公司 Crosslinking agent, full suspension fracturing fluid and preparation method thereof
CN106928959A (en) * 2017-03-27 2017-07-07 成都劳恩普斯科技有限公司 Crosslinking agent, full suspension fracturing fluid and preparation method thereof
CN111171797A (en) * 2018-11-13 2020-05-19 中国石油化工股份有限公司 Cross-linking agent and preparation method thereof
CN109735318A (en) * 2019-01-21 2019-05-10 克拉玛依中科恒信科技有限责任公司 A kind of pressure break enhanced type controllable cross-linking agent and preparation method thereof
CN110437819A (en) * 2019-09-17 2019-11-12 四川洁能锐思石油技术有限公司 A kind of low polymer fracturing fluid and preparation method thereof
CN114437705A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 Organic crosslinking acid and organic aluminum zirconium crosslinking agent for acid fracturing and preparation method thereof
CN115287054A (en) * 2022-08-23 2022-11-04 洲际海峡能源科技有限公司 Organic aluminum crosslinking agent, preparation method thereof and application thereof in continuous mixed fracturing fluid

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