CN102399549B - Rock breaking agent for stabilizing well walls and preparation method thereof - Google Patents
Rock breaking agent for stabilizing well walls and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a rock breaking agent for stabilizing well walls and a preparation method thereof. The rock breaking agent consists of the following components in part by mass: 80 to 100 parts of plant protein, 180 to 200 parts of water, 50 to 65 parts of 20 mass percent n-hexane solution of phosphorus oxychloride, 20 to 40 parts of sulphydryl polyether polyol, 30 to 40 parts of sulfonated dioctyl succinate, 16 to 24 parts of sulfonating agent and pH regulator. The efficient rock breaking agent for stabilizing the well walls can instantaneously and effectively reduce the strength of stratum rock, is favorable for stabilizing the well walls, and improves the drilling speed so as to reduce the exploratory development cost, protect the oil-gas layer and improve the recovery rate.
Description
Technical field
The present invention relates to efficient rock-breaking agent (WGP) of a kind of stabilizing borehole and preparation method thereof.
Background technology
The petroleum engineering operation to as if be imbedded in the dark rocks of underground thousands of rice, rock breaking efficiency is the important technological problems in the petroleum drilling, what its embodied is drilling speed.Drilling speed is the key factor that influences oil field prospecting and development benefit, improves drilling speed and can reduce drilling cost significantly, accelerates the exploratory development process, also is the problem that presses for solution in the deep-well ultra deep well drilling process.Simultaneously, the raising of drilling speed can reduce the time that drilling fluid soaks hydrocarbon zone, reduces drilling fluid to reservoir damage caused, is conducive to find hydrocarbon zone and increases substantially recovery ratio.
An importance of ROCK MECHANICS RESEARCH relates to efficient rock-breaking mechanism and the method for machinery, waterpower and combined-breaking rock in the drilling process; Another importance relates to the problem of wellbore stability after the stress relief of original place, and it comprises that mechanics, chemistry and three factor effects of waterpower are to the influence of wellbore stability.Continuous expansion along with the oil-gas exploration and development field, the stratum that runs in the drilling process becomes increasingly complex, well is more and more darker, the complexcase of down-hole are difficult to expect especially, the difficulty of handling is also increasing, when bore meeting hardpan mud shale, soft shale, sticking shale and swelling shale under the deep well high pressure, this class stratum is easy to the generation that hydration swelling causes the down-hole complex accident, especially at western deep drilling, bore to meet in front of the mountains in the strong stress structure and big section mud shale well section process the performance of borehole well instability problem particularly outstanding.
Aspect oil-gas exploration and development, lack at present at boring to meet and take into account efficient rock-breaking simultaneously and be conducive to the mechanism research of wellbore stability and the research and development of additive for drilling fluid, therefore, develop a cover and can have very important meaning for improving oil gas well exploration and development benefit in effective drilling liquid technology system that reduces formation rock intensity and be conducive to wellbore stability of moment.
Summary of the invention
The purpose of this invention is to provide broken rock agent of a kind of stabilizing borehole and preparation method thereof; broken rock agent can effectively reduce formation rock intensity moment; be beneficial to wellbore stability; thereby solving the borehole wall collapses; fall the problem of piece; improve deep-well ultra deep well drilling speed, and then reduce the exploratory development cost, reduce development risk, protection hydrocarbon zone, the recovery ratio that improves.
The broken rock agent (WGP) of a kind of stabilizing borehole of the present invention is by the phosphorus oxychloride (POCl of mass parts by 80-100 part vegetable-protein, 180-200 part water, 50-65 part mass concentration 20%
3) the sulfydryl polyether glycol, the sulfosuccinate dioctyl ester of 30-40 part, sulphonating agent and the pH value conditioning agent of 16-24 part of hexane solution, 20-40 part form.
The preparation method of a kind of stabilizing borehole efficient rock-breaking agent (WGP): break each composition of rock agent according to the mass fraction, preparation process is as follows:
1) vegetable-protein with 80-100 part joins in 180-200 part water, leave standstill 100-140 minute at normal temperatures after, under constant temperature 45-55 ℃ condition, vibration is evenly;
2) at 40-60 ℃, in the solution of step 1), splash into 16-24 part sulphonating agent, constant temperature stirring reaction 60-80 minute;
3) with step 2) the solution water-bath is heated to 80-100 ℃, is 7-9 with pH regulator agent regulator solution pH value;
4) be made into 20% phosphorus oxychloride solution with the n-hexane dissolution phosphorus oxychloride, take by weighing 50-65 part phosphorus oxychloride solution and add in the step 3) solution constant temperature stirring reaction 80-100 minute;
5) with pH regulator agent regulating step 4) pH value of solution value 7-9, add and be equipped with in the four-hole boiling flask of stirring, thermometer, nitrogen conduit;
6) the sulfydryl polyether glycol of 20-40 part and the sulfosuccinate dioctyl ester of 30-40 part are mixed the composition dropping liquid;
7) stir, logical nitrogen was warming up to 100-120 ℃, and the dropping liquid that sulfydryl polyether glycol and sulfosuccinate dioctyl ester are formed dropwise adds in the solution of step 5), added the agent of polycondensation generation in 1 hour stabilizing borehole efficient rock-breaking at 1～5 hour.
Sulphonating agent is oleum;
PH value conditioning agent is the aqueous sodium hydroxide solution of concentration 30-50%.
The principle of work of stabilizing borehole efficient rock-breaking of the present invention agent:
Drill teeth is pressed into has many microfractures to produce in the process of rock, what the formation rock that bores at first contacted in the drilling process is drilling fluid, because microfracture often has bigger perviousness than the hole in the original rocks, when the crackle in the broken hole of tooth is subjected to water impact, liquid will infiltrate in the crack, at this moment stressing conditions is similar to rigid body chock of wedging in rock in the rock, so be called the water wedging action.Water wedge wedging crackle produces certain stress field, produces the tensile stress concentration zones at crack tip, and it expands crackle rapidly, causes rock further to destroy, thus moment effectively reduce formation rock intensity, can increase substantially rate of penetration.In case but rock continues to soak the long period in drilling fluid, drilling fluid can be from the stress cage effect, suppress two kinds of approach of hydration and strengthen rock strength, thereby guarantee the stability of the borehole wall: on the one hand, drilling fluid can pass through at clay mineral, strong adsorption and change its wettability on the borehole wall, effectively reduce its surface tension, make drilling cuttings, the wettability of borehole wall surface changes to the oleophylic direction from hydrophilic, thereby form the fine and close non-wetting ability plugged zone of one deck, the pressure packing is provided, increased borehole wall belt stress on every side, and make drilling fluid filtrate enter the stratum as few as possible, weaken filtrate and enter influence to rock strength; On the other hand, drilling fluid can prevent that rock strength from reducing by suppressing hydration, turgor pressure increases in the rock because hydration can cause, make that bond weakens between rock particles, rock strength reduces, and the drilling fluid of invading blowhole inside equally can be by the wettability of change and the inner rock surface of hole, reduce the surface tension of rock, its wettability is changed to the oleophylic direction from hydrophilic, suppressed the hydration of core hole inside, thereby can increase rock strength.
The property that this drilling fluid has realizes that by adding the agent of stabilizing borehole efficient rock-breaking therefore, stabilizing borehole efficient rock-breaking agent molecule must possess following characteristic, can be summarized as following several respects:
(1) can adsorb with rock and drilling cuttings, make the wettability of rock, drilling cuttings and rock and hole thereof to the direction transformation of oleophylic;
(2) can infiltrate rapidly in the crackle of rock with higher infiltration rate and big permeation volume;
(3) has good heat-resisting property;
(4) can with drilling fluid system in other treatment agent have excellent compatibility;
(5) can moment effectively reduce bottom rock intensity;
Therefore, stabilizing borehole efficient rock-breaking agent molecule structure will have strong adsorption group, can realize the purpose of orthoselection by grafting phosphate on protein molecule, makes protein molecule strengthen the oriented adsorption function; Increase the length of its hydrocarbyl chain simultaneously, long hydrocarbyl chain can improve the hydrophobic performance that adsorbs back drilling tool drilling cuttings; Because the tertiary structure of protein, protein molecule possess-OH ,-NH
2, functional group such as COOH-and long organic molecule chain, therefore, protein is the optimal selection as main chain, the characteristic that agent need possess according to the stabilizing borehole efficient rock-breaking increases characteristic functional group again and realizes the specific function of stabilizing borehole efficient rock-breaking agent again.
Because along with the increase of drilling depth, formation temperature also raises gradually, protein is as a kind of organic polymer, its heat-resisting property extreme difference wants it is widely used in the drilling fluid system, just must improve its temperature resistance ability, it is carried out sulfonation modifying handle, improve temperature resistance.
Therefore, stabilizing borehole efficient rock-breaking provided by the invention agent, be raw material with the plant protein, again it being carried out sulfonation earlier handles, behind grafting phosphate on its molecular side chain, then with sulfydryl polyether glycol, the polycondensation of sulfosuccinate dioctyl ester, realization is so that infiltration rate and higher permeation volume rapid osmotic are gone into the rock microfracture faster, reduce surface tension and the capillary resistance of rock surface and hole inside, reduce or eliminate the huge chip hold down in shaft bottom, thereby moment is reduced rock strength, efficient rock-breaking; Contain strong adsorption group and hydrophobic grouping in its structure; the inner wettability of rock surface and hole is changed to the direction of oleophylic; thereby strengthen rock strength from stress cage effect, two kinds of approach of inhibition hydration; realize wellbore stability; thereby reduce the exploratory development cost, reduce development risk, protection hydrocarbon zone, the recovery ratio that improves.
The effect of invention
(1) stabilizing borehole efficient rock-breaking agent soak time is to the influence of core intensity
Adopt single shaft, triaxial stress experiment test core adding and do not adding the variation of soaking different time core intensity in the stabilizing borehole efficient rock-breaking agent drilling fluid respectively.Used basic slurry formula is: 4% soil paste+0.1%80A51+0.5% amine salt+1%SPNH+1%FT-1+0.5XY-27.
Can find out that from Fig. 1 and Fig. 2 core does not soak in adding the drilling fluid of WGP, its core intensity reduces gradually along with the prolongation of soak time; When core soaks in the WGP drilling fluid, changing down is faster along with the increase of core soak time for core intensity.The simple stress test result shows core intensity minimum when soak time reaches 30s; The triaxial stress test result shows that core soaks in the drilling fluid of 0.5%WGP, adopt the 10MPa confined pressure, core intensity flex point occurs at 60s, increases confined pressure to 20MPa, core intensity minimum value will occur at 20s, is conducive to the effectively broken rock fast in the drilling process this moment.
(2) this stabilizing borehole efficient rock-breaking agent concentration is to the influence of core intensity
Adopt simple stress, triaxial stress experiment test method to test core soaks core intensity behind the 5s in different concns WGP drilling fluid variation.
Can find out that from Fig. 1 and Fig. 2 WGP concentration and core strength relationship curve are as shown in Figure 1.The initial core intensity that the base slurry is corresponding is higher, and along with the increase of adding WGP concentration, core intensity reduces thereupon, core intensity minimum when WGP concentration is 0.5%; Continue to increase WGP concentration and be unprofitable to reduce core intensity.
(3) this stabilizing borehole efficient rock-breaking agent concentration is to the influence of wellbore stability
Utilize the simple stress experiment test natural core in the WGP drilling fluid, soak the changing conditions of core intensity behind the 12h, test result is as shown in the table.
The influence (soak time 12h) of the wellbore stability of table 1WGP
As can be seen from Table 1, the natural core of same rate of permeation soaks 12h respectively in base slurry and 0.5%WGP drilling fluid, and the core uniaxial compressive strength that the WGP drilling fluid soaks is obviously big than the core that does not add the immersion of WGP drilling fluid, is conducive to wellbore stability.
(4) this stabilizing borehole efficient rock-breaking agent is measured the influence to rate of penetration
Experimental technique: utilize the drilling simulation experimental installation, in constant experiment the pressure of the drill, rotating speed and pump pressure parameter, adopt normal PDC drill bit, triangular polycrystalline diamond diamond head and tooth-wheel bit respectively, creep in different rock simulation drilling wells, obtain and add the actual speed index that creeps in stabilizing borehole efficient rock-breaking agent drilling fluid front and back.
Experiment parameter:
Choose suitable parameters such as constant the pressure of the drill, rotating speed and pump pressure according to the actual situation of creeping into.
Bit diameter: 92mm; The pressure of the drill: 13.62KN;
Rotating speed: 100rpm; Bit pressuredrop: 1MPa,
The agent of stabilizing borehole efficient rock-breaking and drilling fluid proportioning (1: 500)
By under constant experiment the pressure of the drill, rotating speed and pump pressure parameter condition, adopt conventional PDC drill bit, triangular polycrystalline diamond diamond head and tooth-wheel bit respectively, creep in different rock simulation drilling wells, simulate drilling well as drilling fluid and 0.5% steady concentration borehole wall efficient rock-breaking agent as drilling fluid with clear water, influence the results are shown in Table 10.The result shows: stabilizing borehole efficient rock-breaking agent (0.5%) is very remarkable to the amplitude of the rate of penetration raising of wash boring.
Add the influence of the drilling speed of 0.5%WGP in table 1 clear water
Annotate: Kd represents the rock drillability index
To sum up, the agent of stabilizing borehole efficient rock-breaking is to be main chain with protein, again through sulfonation processing, grafting phosphate group, with sulfydryl polyether glycol, the polycondensation of sulfosuccinate dioctyl ester, by the sign to stabilizing borehole efficient rock-breaking agent performance, can draw as drawing a conclusion:
1, the agent of stabilizing borehole efficient rock-breaking can effectively improve rate of penetration.The agent of stabilizing borehole efficient rock-breaking makes its oriented adsorption performance, high temperature resistant property, rapid osmotic ability significantly improve by the design of introducing a large amount of strong oriented adsorption groups and rapid osmotic molecular structure, realization is so that infiltration rate and higher permeation volume rapid osmotic are gone into the rock microfracture faster, reduce surface tension and the capillary resistance of rock surface and hole inside, thereby moment is reduced rock strength, efficient rock-breaking;
2, the effective stabilizing borehole of stabilizing borehole efficient rock-breaking agent.The agent of stabilizing borehole efficient rock-breaking can make the inner wettability of rock surface and hole change to the direction of oleophylic by introducing strong adsorption group and hydrophobic grouping, thereby strengthens rock strength from stress cage effect, two kinds of approach of inhibition hydration, realizes wellbore stability.
In sum; a kind of stabilizing borehole efficient rock-breaking provided by the invention agent (WGP) and manufacturing process thereof; this creeps into agent can significantly improve deep-well ultra deep well drilling speed, thereby reduces the exploratory development cost, reduces development risk, protection hydrocarbon zone, the recovery ratio that improves.
Description of drawings
The test of Fig. 1 a soak time vs core intensity simple stress.
The test of Fig. 1 b soak time vs core intensity triaxial stress.
The test of Fig. 2 a WGP concentration vs core intensity (5s immersion) simple stress.
The test of Fig. 2 bWGP concentration vs core intensity (5s immersion) triaxial stress.
Embodiment
Embodiment 1
A kind of stabilizing borehole efficient rock-breaking agent (WGP) comprises the phosphorus oxychloride (POCl of concentration 20% of 50 parts of water, the mass fractions of 180 parts of 80 parts of vegetable-proteins of mass fraction, mass fraction
3) sulphonating agent, normal hexane and the pH value conditioning agent of 16 parts of sulfosuccinate dioctyl ester, mass fractions of 30 parts of sulfydryl polyether glycol, mass fractions of 20 parts of solution, mass fractions.
A kind of manufacturing process of synthetic this stabilizing borehole efficient rock-breaking agent (WGP):
1) take by weighing vegetable-protein and be added to the water, leave standstill 100 minutes at normal temperatures after, under 45 ℃ of conditions of constant temperature, vibration is evenly;
2) with above-mentioned solution at 40 ℃, take by weighing sulphonating agent, splash into constant temperature stirring reaction 60 minutes;
3) above-mentioned solution water-bath being heated to 80 ℃, is 7 with pH regulator agent regulator solution pH value;
4) be made into 20% phosphorus oxychloride solution with the n-hexane dissolution phosphorus oxychloride, take by weighing phosphorus oxychloride solution and add constant temperature stirring reaction 80 minutes;
5) with pH regulator agent regulator solution pH value 7, add and be equipped with in the four-hole boiling flask of stirring, thermometer, nitrogen conduit;
6) take by weighing sulfydryl polyether glycol and sulfosuccinate dioctyl ester, mix the back and form dropping liquid;
7) stir, logical nitrogen was warming up to 100 ℃, and the dropping liquid that sulfydryl polyether glycol and sulfosuccinate dioctyl ester are formed dropwise adds above-mentioned solution, added the agent of polycondensation generation in 1 hour stabilizing borehole efficient rock-breaking at 1 hour.
Sulphonating agent is oleum;
PH value conditioning agent is the aqueous sodium hydroxide solution of concentration 30%.
Embodiment 2
A kind of broken rock agent (WGP) of stabilizing borehole comprises the phosphorus oxychloride (POCl of 100 parts of vegetable-proteins, 200 parts of water, 65 parts of concentration 20% by mass parts
3) hexane solution, 40 parts sulfydryl polyether glycol, 40 parts sulfosuccinate dioctyl ester, 24 parts sulphonating agent pH value conditioning agent.
A kind of manufacturing process of synthetic this stabilizing borehole efficient rock-breaking agent (WGP):
1) take by weighing vegetable-protein and be added to the water, leave standstill 140 minutes at normal temperatures after, under 60 ℃ of conditions of constant temperature, vibration is evenly;
2) with above-mentioned solution at 60 ℃, take by weighing sulphonating agent, splash into constant temperature stirring reaction 80 minutes;
3) above-mentioned solution water-bath being heated to 100 ℃, is 9 with pH regulator agent regulator solution pH value;
4) be made into 20% phosphorus oxychloride solution with the n-hexane dissolution phosphorus oxychloride, take by weighing phosphorus oxychloride solution and add constant temperature stirring reaction 80-100 minute;
5) with pH regulator agent regulator solution pH value 9, add and be equipped with in the four-hole boiling flask of stirring, thermometer, nitrogen conduit;
6) take by weighing sulfydryl polyether glycol and sulfosuccinate dioctyl ester, mix the back and form dropping liquid;
7) stir, logical nitrogen was warming up to 120 ℃, and the dropping liquid that sulfydryl polyether glycol and sulfosuccinate dioctyl ester are formed dropwise adds above-mentioned solution, added the agent of polycondensation generation in 1 hour stabilizing borehole efficient rock-breaking at 5 hours.
Sulphonating agent is oleum;
PH value conditioning agent is the aqueous sodium hydroxide solution of concentration 50%.
Embodiment 3
This stabilizing borehole efficient rock-breaking agent is pressed mass fraction and is made up of the hexane solution of the phosphorus oxychloride of 90 parts vegetable-protein, 190 parts water, 60 parts of mass concentrations 20%, 30 parts sulfydryl polyether glycol, 35 parts sulfosuccinate dioctyl ester, 20 parts sulphonating agent and pH value conditioning agent.
The preparation method of the broken rock agent of stabilizing borehole is characterized in that:
1) take by weighing vegetable-protein and be added to the water, leave standstill 120 minutes at normal temperatures after, under the condition of 50 ℃ of constant temperature, vibration is evenly;
2) with above-mentioned solution at 50 ℃, take by weighing sulphonating agent, splash into constant temperature stirring reaction 70 minutes;
3) above-mentioned solution water-bath being heated to 90 ℃, is 8 with pH regulator agent regulator solution pH value;
4) be made into 20% phosphorus oxychloride solution with the n-hexane dissolution phosphorus oxychloride, take by weighing phosphorus oxychloride solution and add constant temperature stirring reaction 90 minutes;
5) with pH regulator agent regulator solution pH value 8, add and be equipped with in the four-hole boiling flask of stirring, thermometer, nitrogen conduit;
6) take by weighing sulfydryl polyether glycol and sulfosuccinate dioctyl ester, mix the back and form dropping liquid;
7) stir, logical nitrogen was warming up to 110 ℃, and the dropping liquid that sulfydryl polyether glycol and sulfosuccinate dioctyl ester are formed dropwise adds above-mentioned solution, added the agent of polycondensation generation in 1 hour stabilizing borehole efficient rock-breaking at 4 hours.
Claims (6)
1. the broken rock agent of a stabilizing borehole is characterized in that: press mass fraction and be made up of the hexane solution of the phosphorus oxychloride of the water of the vegetable-protein of 80-100 part, 180-200 part, 50-65 part mass concentration 20%, the sulfydryl polyether glycol of 20-40 part, the sulfosuccinate dioctyl ester of 30-40 part, sulphonating agent and the pH value conditioning agent of 16-24 part.
2. the broken rock agent of stabilizing borehole according to claim 1, it is characterized in that: described sulphonating agent is oleum.
3. the broken rock agent of stabilizing borehole according to claim 1 is characterized in that: described pH value conditioning agent is the aqueous sodium hydroxide solution of mass concentration 30-50%.
4. the preparation method of the broken rock agent of a stabilizing borehole as claimed in claim 1 is characterized in that: broken each composition of rock agent according to the mass fraction, preparation process is as follows:
1) vegetable-protein with 80-100 part joins in 180-200 part water, leave standstill 100-140 minute at normal temperatures after, under constant temperature 45-55 ℃ condition, vibration is evenly;
2) at 40-60 ℃, in the solution of step 1), splash into 16-24 part sulphonating agent, constant temperature stirring reaction 60-80 minute;
3) with step 2) the solution water-bath is heated to 80-100 ℃, is 7-9 with pH regulator agent regulator solution pH value;
4) be made into 20% phosphorus oxychloride solution with the n-hexane dissolution phosphorus oxychloride, take by weighing mass fraction 50-65 part phosphorus oxychloride solution and add in the step 3) solution constant temperature stirring reaction 80-100 minute;
5) with pH regulator agent regulating step 4) pH value of solution value 7-9, add and be equipped with in the four-hole boiling flask of stirring, thermometer, nitrogen conduit;
6) the sulfydryl polyether glycol of 20-40 part and the sulfosuccinate dioctyl ester of 30-40 part are mixed the composition dropping liquid;
7) stir, logical nitrogen was warming up to 100-120 ℃, and the dropping liquid that sulfydryl polyether glycol and sulfosuccinate dioctyl ester are formed dropwise adds in the solution of step 5), added the agent of polycondensation generation in 1 hour stabilizing borehole efficient rock-breaking at 1～5 hour.
5. preparation method according to claim 4, it is characterized in that: described sulphonating agent is oleum.
6. preparation method according to claim 4, it is characterized in that: described pH value conditioning agent is the aqueous sodium hydroxide solution of concentration 30-50%.
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| CN101186812A (en) * | 2007-12-12 | 2008-05-28 | 中国石油集团钻井工程技术研究院 | Fast drilling agent formulation and preparation technique thereof |
| CN101186813A (en) * | 2007-12-28 | 2008-05-28 | 中国石油集团钻井工程技术研究院 | Fast drilling fluid and preparation technique thereof |
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| CN101186812A (en) * | 2007-12-12 | 2008-05-28 | 中国石油集团钻井工程技术研究院 | Fast drilling agent formulation and preparation technique thereof |
| CN101186813A (en) * | 2007-12-28 | 2008-05-28 | 中国石油集团钻井工程技术研究院 | Fast drilling fluid and preparation technique thereof |
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