Synthesis and applicat...
1970-01-01 08:00Source:
Polyamine is in recent years at home and abroad emerging a drilling fluid inhibitor and Baker Hughes research and development of the system of HPWBM and Magcobar company ultradrill system are to polyamine as the core processing agent of water-based drilling fluid performance close to the oil base drilling fluid, the environment better compatibility. After 2007, China has carried out the research of polyamine inhibitors, and some products have been widely used. In 2013, the author of the research team independently synthesized the first generation of polyamine inhibitors JY-1. But in the experiment, it is found that the temperature resistance of JY-1 is poor, and the performance is not stable. Through micro analysis that JY-1 backbone containing ether bond structure in strong acid and strong alkali environment easily protonated or fracture, generally at a temperature higher than 120 DEG C when inhibition was significantly reduced. On the basis of deep analysis of the first generation polyamine inhibitor JY-1, the molecular structure was redesigned, and a high temperature resistant and salt resistant shale inhibitor JY-2 was synthesized through two steps.
After the completion of the indoor synthesis, to enlarge the production process was explored, the use of 1t reactor in the workshop synthesis inhibitor JY-2.
1.4 performance testing of synthetic products
1.4.1 infrared spectroscopy (FT-IR) test
Using Nicolet-Nexus670 type Fourier transform infrared spectrometer, using KBr compression method for the synthesis of FT-IR test results, the results shown in figure 6.
As shown in Figure 6, 3371.94cm-1 is a non associative N-H contraction vibration absorption peak; 2989.56cm-1 for the -C group stretching vibration absorption peak; 600 ~ 750cm-1 for -NH, the surface vibration absorption band. It can be seen that the molecular chain has the initial design of molecular groups, and does not contain easy to break the ether oxygen key, so the structure of the target product and design.
1.4.2 liquid / mass spectrometry test
The United States Finnigan mass produced the LCQ DecaXP type liquid / matter combined with instrument, the synthetic samples of liquid chromatography-mass spectrometry test. It is speculated that produce molecular formula: C23H66N7O4.
Testing of 1.4.3 molecular weight distribution
The molecular weight distribution of the synthesized samples was determined by Agilent 1200 liquid chromatography and TSK-GEL gel filtration chromatography column. The test results show that the molecular weight of the synthesized samples is 508g/moL, the molecular weight distribution is relatively concentrated, which indicates that the reaction conditions are suitable, and the side effects are suppressed effectively, and the yield is higher.
2 performance evaluation of synthetic products
2.1 resistance to temperature
The mass concentration is 1% of JY-1 or jy-2 solution respectively under the different temperature ageing rolling 16h, adds the bentonite bentonite powder with 6% bentonite slurry, after 24h water quantity to take 50ml soil slurry into the centrifugal tube ultracentrifugation experiments, through centrifugal tube after observation of centrifugal clear liquid volume and bottom mud cake density judgment inhibitor temperature resistance, and the results are shown in Table 1. From table 1 shows, JY-1 in temperature more than 120 DEG C, inhibition decreased and jy-2 within the range of normal temperature to 180 DEG C centrifugal results are basically the same, indicating that the second generation of polyamine jy-2 anti temperature greatly increased to 180 DEG C temperature resistance, wide range of applicable temperature.
2.2 inhibition
Using high speed centrifugation, inhibiting clay slurry making method, laser particle size analysis and rolling recovery experiments of jy-2 for evaluating the inhibition, and Ultrahib and Magcobar mud company, China UHIB, PF-HCS similar products inhibitory were compared.
2.2.1 high speed centrifugal method
In the mass concentration of 1% different inhibitor solution to add sodium bentonite, with 6% bentonite slurry, 24h after the hydration of high speed centrifugal experiment (with water to do comparison). Do 4 parallel samples, take the average drawing. The volume of water, JY-2, Ultrahib, UHIB and PF-HCS were 6.5, 42.56, 42.2, 34.5, 35.8mL, respectively. From this, we can know that the JY-2 solution in the centrifugal water and Ultrahib solution in the centrifugal water quite, than the UHIB solution and PF-HCS solution in the centrifugal water.
2.2.2 inhibiting clay pulp making method
In the inhibitor solution of 400mL mass concentration of 1%, 5% soil powder was added, the rheological property of 16h was measured at 100 degrees C, and then the 5% soil powder was added to the soil. The apparent viscosity for the vertical axis, with the number of soil powder as the abscissa mapping results shown in figure 7. As is shown in Fig 7, jy-2 solution join silt times most apparent viscosity of the growth trend of the slow, indicating that the synthesis of jy-2 can effectively inhibit clay hydration dispersion, slightly higher than the Ultrahib anti pollution ability of clay, in the drilling process can effectively prevent shale formation shrinkage complex.
2.2.3 laser particle size analysis
At the concentration of 1% different inhibitor solution, adding aperture 75gm sieve and drying of sodium bentonite, with 6% of bentonite slurry and placed in a horizontal position on the oscillator, each interval of 2h, oscillating 30min, from the beginning of the oscillation time, after 24h rehydration were laser particle size analysis, respectively read d0.1, tap, d0.9 value and D[4] (volume average particle diameter, the cumulative distribution of 43% corresponding to the particle diameter). The method can be used to distinguish the inhibition of the treatment agent from the microscopic angle, and the experimental results are shown in table 2. From table 2 shows, jy-2 size value and volume average particle size and Ultrahib similar to, far more than other inhibitors that jy-2 solution of silt particles water of dispersion degree is very small, can effectively inhibit the hydration of clay particles, can affect the performance of the drilling fluid to prevent drilling process due to the shale cuttings dispersion and migration.
2.2.4 rolling recovery test
Selection of Daqing shallow Yaojia group a mud shale detritus (diameter of 2.0 ~ 3.2min), respectively into filled with 350ml water and 1% different poly amine inhibitor solution of high temperature aging tank and rolling recovery experiments, the aperture is 0.45 mm sieve, the results shown in Figure 8. Is shown in Fig 8. Jy-2 a recovery rate and Ultrahib similar, than the Chinese two poly amines were much higher, indicating the strongest suppression jy-2; rate of jy-2 secondary recovery rate and recovery of three times with a recovery rate of close to, was higher than that in the Ultrahib and other samples, that jy-2 firmly in cuttings to the surface adsorption, long duration of action, namely long-term suppression of jy-2 strong, in the drilling process can maintain long-term stability of borehole wall.
2.3 influence of rheological property of drilling fluid
Jy-2 instead of Daqing oil field current silicon-based cationic fresh drilling mud and Xinjiang East Tarim Oilfield inhibitor KCl brine drilling fluid, and by adding different amount of added to the system, measuring the performance of drilling fluid, the results are shown in Table 3 and table 4. From table 3, table 4 shows, in silicon-based cationic freshwater system and Tadong brine system added (0.5% ~ 2%) 2, on the rheological property of drilling fluid had no effect, filter loss and decreased system suppression greatly raise. So, the compatibility of JY-2 with fresh water system and KCl brine system is good.
2.4 biological toxicity test
The biological toxicity test results showed that the EC50 was more than 12000mg/L. Therefore, the sample is non-toxic and can meet the requirements of environmental protection.
3 on site application
To polyamine inhibitors jy-2 substituted inhibitors in raw water base drilling fluid system, and 1.0% ~ 1.5% and formed new system in Daqing Qijia Gulong sag in the southern tip of the ancient 693-104- flat 104 well in field application. The well drilling depth is 2728m, the horizontal displacement is 1043.26m, and the horizontal segment is long 768m. The well drilling in the Nenjiang formation and the formation of the Yao family, including two sections of the soft formation of the large section of the mudstone, water absorption is very easy to occur after the expansion and contraction of water, resulting in drilling mud package and card drilling phenomenon, but also easy to cause suction blowout. The well target layer in the Yao family group, more than 750m of the level of operation are all in the Yao family group. The formation of mudstone is also very easy to be hydrated dispersion, water roll recovery is only 6.81%, the drilling fluid inhibition of put forward very high requirements. The well 957m from the well depth of two open operations, the specific construction process is as follows.
1) straight well section. The drilling in the straight well is two, and the soft part is a large section of mudstone. JY-2 addition of the inhibitor in drilling fluid was 1%, which fully guaranteed the drilling fluid inhibition ability of shale. There is no shrinkage and drilling accident in drilling, and the cutting edges and corners of the vibrating screen are clear, which indicates that JY-2 has a good inhibiting effect.
2) the inclined section. In the Nenjiang group began to build, after entering the inclined section, the drilling fluid to be on time to add the inhibitor, and uniform to join, join 25kgJY-2 per 100m, in order to maintain the drilling fluid inhibition. Vibration sieve on the back of debris forming, particle rules, there is no peeling off the block and other phenomena.
3) horizontal section. Due to horizontal section in a very easy water scattered Yaojia formation, the drilling fluid must ensure the strong inhibition, joined the 50kgJY-2 per 100m, drilling fluid jy-2 plus the amount of not less than 1.5%. In drilling process, the formation of cuttings and the rule of particles did not occur in the original system.
The performance of the well drilling fluid is shown in table 5. As seen from table 5, JY-2 and drilling fluid compatibility is good, in the horizontal section of JY-2 increase, the performance of drilling fluid is stable, there is no fluctuation phenomenon. The outstanding inhibition ability of JY-2 ensures the smooth completion of the well, the average well diameter is 7.1%, and the average mechanical drilling speed is 7.11m/h. The field construction shows that the inhibition ability of polyamine inhibitor JY-2 is prominent, which can meet the requirement of drilling in large section of mudstone formation.
4 conclusions
1 based on the analysis of the molecular structure of the first generation polyamine inhibitor JY-1, the molecular structure was redesigned, and the high temperature stability of the inhibitor was synthesized. By means of infrared spectrum analysis, the synthetic samples are not easy to break the molecular structure, moderate molecular weight, good environmental compatibility.
2. By high speed centrifugation, and laser particle size analyzer, macro and micro combined with indoor experiment proved that samples synthesized the inhibition and equal to that of foreign products, than China poly amine product inhibition is strong, can effectively inhibit shale hydration and dispersion, and long-term strong inhibition, good compatibility with fresh water and salt water drilling fluid compatibility, and help to reduce the drilling fluid loss.
3. Poly amine inhibitor jy-2 application in ancient 693.104. flat 104 wells show that, the poly amine inhibitor can be used to improve the high shale content in formation of wellbore stability can also be to provide technical support for the development of unconventional oil and gas resources.
1 development of high effective mudstone inhibitor
1.1 principles for the design of molecular structure of novel inhibitors
In order to improve the stability and inhibitors of temperature resistance, molecular structure of JY-1 was redesigned and improved. The principle is as follows: the backbone structure of a stable, using C - C, C - N chain instead of ether oxygen bond in the main chain of JY-1, improve the high-temperature stability of polyamine; inhibition of the strong, to further increase the job amine and secondary amine groups on the main chain number, improve the inhibition ability of products to shale; the proper molecular chain length, appropriate molecular weight is an important premise to guarantee the inhibition and low toxicity; compatibility of good, does not contain functional groups with other additives for drilling fluid reaction, improve the compatibility of drilling fluid at the same time, can maintain the stability of the structure under strong alkaline conditions.
1.2 synthesis of novel inhibitors
1) polyol, certain amount of metal catalysts are added in the high temperature and high pressure reaction kettle, high purity hydrogen pressure stability in between 2.6 to 3.2 MPa, and then slowly add a certain amount of high purity ammonia, warming up to 220 to 240 DEG C and remained stable in the mixing of high temperature reaction of 4 ~ 5h. After the reaction, the product can be filtered and dehydrated, and the polymer intermediate containing ether bond can be obtained. The specific reaction process is as follows.
2) in the intermediate join a certain amount of reducing agent, in 160 to 180 DEG C under the condition of reaction 2 ~ 3H, the polymer intermediates from the ether bond cleavage, and at the break introduced amine. To get light brown, have a certain viscosity of low molecular weight polymer inhibitors, replace No. 2.
1.3 determination of the optimal synthesis conditions
The effects of reaction temperature, reaction time, amount of catalyst, the amount of monomer and the amount of reducing agent on the product inhibition performance were investigated, and the results are shown in Figure 1 to 5.
After the completion of the indoor synthesis, to enlarge the production process was explored, the use of 1t reactor in the workshop synthesis inhibitor JY-2.
1.4 performance testing of synthetic products
1.4.1 infrared spectroscopy (FT-IR) test
Using Nicolet-Nexus670 type Fourier transform infrared spectrometer, using KBr compression method for the synthesis of FT-IR test results, the results shown in figure 6.
As shown in Figure 6, 3371.94cm-1 is a non associative N-H contraction vibration absorption peak; 2989.56cm-1 for the -C group stretching vibration absorption peak; 600 ~ 750cm-1 for -NH, the surface vibration absorption band. It can be seen that the molecular chain has the initial design of molecular groups, and does not contain easy to break the ether oxygen key, so the structure of the target product and design.
1.4.2 liquid / mass spectrometry test
The United States Finnigan mass produced the LCQ DecaXP type liquid / matter combined with instrument, the synthetic samples of liquid chromatography-mass spectrometry test. It is speculated that produce molecular formula: C23H66N7O4.
Testing of 1.4.3 molecular weight distribution
The molecular weight distribution of the synthesized samples was determined by Agilent 1200 liquid chromatography and TSK-GEL gel filtration chromatography column. The test results show that the molecular weight of the synthesized samples is 508g/moL, the molecular weight distribution is relatively concentrated, which indicates that the reaction conditions are suitable, and the side effects are suppressed effectively, and the yield is higher.
2 performance evaluation of synthetic products
2.1 resistance to temperature
The mass concentration is 1% of JY-1 or jy-2 solution respectively under the different temperature ageing rolling 16h, adds the bentonite bentonite powder with 6% bentonite slurry, after 24h water quantity to take 50ml soil slurry into the centrifugal tube ultracentrifugation experiments, through centrifugal tube after observation of centrifugal clear liquid volume and bottom mud cake density judgment inhibitor temperature resistance, and the results are shown in Table 1. From table 1 shows, JY-1 in temperature more than 120 DEG C, inhibition decreased and jy-2 within the range of normal temperature to 180 DEG C centrifugal results are basically the same, indicating that the second generation of polyamine jy-2 anti temperature greatly increased to 180 DEG C temperature resistance, wide range of applicable temperature.
2.2 inhibition
Using high speed centrifugation, inhibiting clay slurry making method, laser particle size analysis and rolling recovery experiments of jy-2 for evaluating the inhibition, and Ultrahib and Magcobar mud company, China UHIB, PF-HCS similar products inhibitory were compared.
2.2.1 high speed centrifugal method
In the mass concentration of 1% different inhibitor solution to add sodium bentonite, with 6% bentonite slurry, 24h after the hydration of high speed centrifugal experiment (with water to do comparison). Do 4 parallel samples, take the average drawing. The volume of water, JY-2, Ultrahib, UHIB and PF-HCS were 6.5, 42.56, 42.2, 34.5, 35.8mL, respectively. From this, we can know that the JY-2 solution in the centrifugal water and Ultrahib solution in the centrifugal water quite, than the UHIB solution and PF-HCS solution in the centrifugal water.
2.2.2 inhibiting clay pulp making method
In the inhibitor solution of 400mL mass concentration of 1%, 5% soil powder was added, the rheological property of 16h was measured at 100 degrees C, and then the 5% soil powder was added to the soil. The apparent viscosity for the vertical axis, with the number of soil powder as the abscissa mapping results shown in figure 7. As is shown in Fig 7, jy-2 solution join silt times most apparent viscosity of the growth trend of the slow, indicating that the synthesis of jy-2 can effectively inhibit clay hydration dispersion, slightly higher than the Ultrahib anti pollution ability of clay, in the drilling process can effectively prevent shale formation shrinkage complex.
2.2.3 laser particle size analysis
At the concentration of 1% different inhibitor solution, adding aperture 75gm sieve and drying of sodium bentonite, with 6% of bentonite slurry and placed in a horizontal position on the oscillator, each interval of 2h, oscillating 30min, from the beginning of the oscillation time, after 24h rehydration were laser particle size analysis, respectively read d0.1, tap, d0.9 value and D[4] (volume average particle diameter, the cumulative distribution of 43% corresponding to the particle diameter). The method can be used to distinguish the inhibition of the treatment agent from the microscopic angle, and the experimental results are shown in table 2. From table 2 shows, jy-2 size value and volume average particle size and Ultrahib similar to, far more than other inhibitors that jy-2 solution of silt particles water of dispersion degree is very small, can effectively inhibit the hydration of clay particles, can affect the performance of the drilling fluid to prevent drilling process due to the shale cuttings dispersion and migration.
2.2.4 rolling recovery test
Selection of Daqing shallow Yaojia group a mud shale detritus (diameter of 2.0 ~ 3.2min), respectively into filled with 350ml water and 1% different poly amine inhibitor solution of high temperature aging tank and rolling recovery experiments, the aperture is 0.45 mm sieve, the results shown in Figure 8. Is shown in Fig 8. Jy-2 a recovery rate and Ultrahib similar, than the Chinese two poly amines were much higher, indicating the strongest suppression jy-2; rate of jy-2 secondary recovery rate and recovery of three times with a recovery rate of close to, was higher than that in the Ultrahib and other samples, that jy-2 firmly in cuttings to the surface adsorption, long duration of action, namely long-term suppression of jy-2 strong, in the drilling process can maintain long-term stability of borehole wall.
2.3 influence of rheological property of drilling fluid
Jy-2 instead of Daqing oil field current silicon-based cationic fresh drilling mud and Xinjiang East Tarim Oilfield inhibitor KCl brine drilling fluid, and by adding different amount of added to the system, measuring the performance of drilling fluid, the results are shown in Table 3 and table 4. From table 3, table 4 shows, in silicon-based cationic freshwater system and Tadong brine system added (0.5% ~ 2%) 2, on the rheological property of drilling fluid had no effect, filter loss and decreased system suppression greatly raise. So, the compatibility of JY-2 with fresh water system and KCl brine system is good.
2.4 biological toxicity test
The biological toxicity test results showed that the EC50 was more than 12000mg/L. Therefore, the sample is non-toxic and can meet the requirements of environmental protection.
3 on site application
To polyamine inhibitors jy-2 substituted inhibitors in raw water base drilling fluid system, and 1.0% ~ 1.5% and formed new system in Daqing Qijia Gulong sag in the southern tip of the ancient 693-104- flat 104 well in field application. The well drilling depth is 2728m, the horizontal displacement is 1043.26m, and the horizontal segment is long 768m. The well drilling in the Nenjiang formation and the formation of the Yao family, including two sections of the soft formation of the large section of the mudstone, water absorption is very easy to occur after the expansion and contraction of water, resulting in drilling mud package and card drilling phenomenon, but also easy to cause suction blowout. The well target layer in the Yao family group, more than 750m of the level of operation are all in the Yao family group. The formation of mudstone is also very easy to be hydrated dispersion, water roll recovery is only 6.81%, the drilling fluid inhibition of put forward very high requirements. The well 957m from the well depth of two open operations, the specific construction process is as follows.
1) straight well section. The drilling in the straight well is two, and the soft part is a large section of mudstone. JY-2 addition of the inhibitor in drilling fluid was 1%, which fully guaranteed the drilling fluid inhibition ability of shale. There is no shrinkage and drilling accident in drilling, and the cutting edges and corners of the vibrating screen are clear, which indicates that JY-2 has a good inhibiting effect.
2) the inclined section. In the Nenjiang group began to build, after entering the inclined section, the drilling fluid to be on time to add the inhibitor, and uniform to join, join 25kgJY-2 per 100m, in order to maintain the drilling fluid inhibition. Vibration sieve on the back of debris forming, particle rules, there is no peeling off the block and other phenomena.
3) horizontal section. Due to horizontal section in a very easy water scattered Yaojia formation, the drilling fluid must ensure the strong inhibition, joined the 50kgJY-2 per 100m, drilling fluid jy-2 plus the amount of not less than 1.5%. In drilling process, the formation of cuttings and the rule of particles did not occur in the original system.
The performance of the well drilling fluid is shown in table 5. As seen from table 5, JY-2 and drilling fluid compatibility is good, in the horizontal section of JY-2 increase, the performance of drilling fluid is stable, there is no fluctuation phenomenon. The outstanding inhibition ability of JY-2 ensures the smooth completion of the well, the average well diameter is 7.1%, and the average mechanical drilling speed is 7.11m/h. The field construction shows that the inhibition ability of polyamine inhibitor JY-2 is prominent, which can meet the requirement of drilling in large section of mudstone formation.
4 conclusions
1 based on the analysis of the molecular structure of the first generation polyamine inhibitor JY-1, the molecular structure was redesigned, and the high temperature stability of the inhibitor was synthesized. By means of infrared spectrum analysis, the synthetic samples are not easy to break the molecular structure, moderate molecular weight, good environmental compatibility.
2. By high speed centrifugation, and laser particle size analyzer, macro and micro combined with indoor experiment proved that samples synthesized the inhibition and equal to that of foreign products, than China poly amine product inhibition is strong, can effectively inhibit shale hydration and dispersion, and long-term strong inhibition, good compatibility with fresh water and salt water drilling fluid compatibility, and help to reduce the drilling fluid loss.
3. Poly amine inhibitor jy-2 application in ancient 693.104. flat 104 wells show that, the poly amine inhibitor can be used to improve the high shale content in formation of wellbore stability can also be to provide technical support for the development of unconventional oil and gas resources.
