CN105670574A - Drilling fluid ether-amine compound inhibitor and preparation method thereof - Google Patents
Drilling fluid ether-amine compound inhibitor and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a drilling fluid ether-amine compound inhibitor and a preparation method thereof. The drilling fluid ether-amine compound inhibitor includes an amine-terminated polyether, a polymeric alcohol, potassium chloride and water. The preparation method is as follows: 10 parts to 25 parts by weight of the potassium chloride are added into 40 to 100 parts of water, and fully mixed at room temperature; then 60 to 100 parts of the amine-terminated polyether is added, and fully mixed at room temperature; the mixture is added into 40 to 80 parts of the polymeric alcohol, and evenly stirred at 25-40 DEG C to obtain the product. The drilling fluid ether-amine compound inhibitor has the characteristics of low foaming ratio, strong inhibition and strong adaptability, can be well compatible with a variety of drilling fluids, greatly reduces the foaming ratio of an organic amine inhibitor, and facilitates field application to a large extent.
Description
Technical field
The present invention relates to shale control agent and preparation method thereof field in Process of Oil Well Drilling, specifically a kind of drilling fluid ether amines composite inhibitor and preparation method thereof.
Background technology
Amine (ammonium) class material is used for suppressing Shale Hydration to expand, improving the history that property of drilling fluid is existing very long, its kind development, successively experienced by the developmental stage of ammonium chloride, ammonium salt, quaternary ammonium cation polymer, partially hydrolyzed polyacrylamide (PHPA), organic cation material-Ji alkylamine, organic cation material-Ji hydroxylamine, both sexes poly-amino acid, alkyl diamine, polyamine glycols and polyether amine. What research both at home and abroad was more at present is second filial generation organic amine inhibitors (alkyl diamine, polyamine glycols and polyether amine), it can overcome, and environmental pollution that conventional quaternary ammonium salts etc. exists, temperature resistance be poor, electropositive crosses high inherent shortcoming, and there is the advantages such as consumption few, instant effect, strong inhibition capability, thus extensively praised highly. Around the high performance water-based drilling fluid (HighPerformanceWaterBasedMud centered by organic amine inhibitors; HPWBM) there is the performance equaling to oil base drilling fluid; ensure that work progress wellbore stability, well clean, in drilling construction safety, raising rate of penetration, reservoir protection etc., all there is pure advantage.
Ether amine substance, as current organic amine inhibitors study hotspot, obtains drilling well industry extensive concern. Its suppression shale hydration mechanism is: current studied polyetheramine and modifier molecular weight thereof are mostly between 200-800, its molecule can enter clay interlayer under the driving of difference in chemical potential and be adsorbed on clay sheet surfaces, by protonating in amido and clay surface negative charge, reduce the Zeta potential of clay particle; Polyetheramine molecule forms hydrogen bond with clay surface silicon oxyalkyl, further the strengthening absorption on clay surface. The combined effect of both electrostatic attraction and hydrogen bond reduces clay interlayer aquation repulsion, reduces clay aquation interlamellar spacing to greatest extent, is bound together by clay lamella, side by side extruding part adsorbed water, weakens clay aquation. Meanwhile, after polyetheramine is adsorbed on clay particle surface, the hydrophobic part of its molecule covers clay surface, reduces the hydrophilic on clay surface, stops the entrance of hydrone, suppresses clay hydration swelling further.Comparing to tradition organic amine inhibitors, ether amines class inhibitor has the advantages such as long-lasting, stability, gentle property and the strong rejection capability of its uniqueness. Its erosion resistibility is strong, it is ensured that drillng operation also has long stratum inhibition after terminating; Temperature resistance good stability, still has good rheological characteristic, leak-off and lubricity under high-temperature high-density; Good with conventional drilling liquid inorganic agent compatibility, it is not result in the jumping phenomenons such as flocculation.
Zhang Guo etc. (CN103087691A) are with polyetheramine for raw material, under base metal catalysts exists with epoxide 90-110 DEG C, be obtained by reacting a kind of organic amine inhibitors with unique molecular structure under vacuum condition, its " distant claw type " diamidogen or polyamine compounds structure can rely on the fixing clay wafer of the two or more amidos of head and the tail, play the aminated compounds inhibitory action to clay better; This inhibitor can be used for the volatile layer quietly of high temperature strong retraction, and anti-Xuanhua bentonite pollutes up to 30%, and landwaste rolls the response rate up to more than 90%, and 8h shale linear expansion rate is within 10%, and temperature resistance reaches 180 DEG C, and bio-toxicity is low, LC50Value, more than 38010mg/L, can be used in deepwater drilling.
Wang Fuhua etc. (Gong Jiaqin. high inhibition water-base drilling fluid formula development and performance evaluation [D]. Qingdao: China University Of Petroleum Beijing, 2011.) utilize dodecyl alcohol synthesizing polyether alcohol, then generating polyethers chloride with chlorination reagent reaction, polyethers chloride obtains polyetheramine with polyethylene polyamine reaction again; Then pass through polyetheramine and oxirane, expoxy propane, epoxy butane mixture reaction obtain the organic amine molecule of same " distant claw type " structure, it has been carried out performance evaluation, and preferably obtain high inhibition water-based drilling formula of liquid, it is being stained with north 3-B and is being stained with Bei3-CJing and carries out on-the-spot test, result shows that this drilling fluid has good suppression shale hydration and expands and scattered ability, to solving because aquation is uneven or the haircut of microcrack layer is educated the hole collapse caused and had good wellbore stability effect.
The units such as Research Institute of Nanjing Chemical Industry Group successfully develops polyetheramine inhibitor NH-1, is widely applied at Henan Oil Field, Jianghan Oil-field, Jiangsu oilfield, China University Of Petroleum Beijing and enterprise also have been developed that relevant ether amines modifiies series products.
But, one of major obstacle of restriction organic amine inhibitors popularization and application is bubble problem, the wellbore constructions such as Shengli Oil Field Lin Pan street 5 well, flat 1 well of justice 123-and Henan peace HF1 well find to add and after organic amine inhibitors circulates one week, produces a large amount of bubble, and use defoamer DeGrain. There is same problem in applying at the scene in ether amines class inhibitor: the polyhydroxy amine based compound of similar polyetheramine adds water base drilling fluid system can produce a large amount of bubble, the bubble formed is small, and add polyetheramine and often make system viscosity raise, this all makes bubble be difficult to eliminate. By aforementioned ether amines class inhibitor product test is found its add 10% bentonite slurry after blistering rate all more than 57.14%. Current each drilling company mainly adopts the method that white oil together mixes addition with organic amine inhibitors at the scene so as to bubble minimum, but effect is still good not.
Summary of the invention
A kind of drilling fluid ether amines composite inhibitor with low blistering rate, strong rejection capability, strong adaptability that it is an object of the invention to overcome the deficiencies in the prior art and provide and preparation method thereof.
The present invention reaches by the following technical programs:
A kind of drilling fluid ether amines composite inhibitor, including the component of following weight proportion:
Wherein, described ending amino polyether is general molecular formula is H2N―R―(OR1)N―NH2Polyoxyethylene ether diamine, R and R in general molecular formula1Being have 3 to 6 different carbon atom numbers or same carbon atoms number purpose alkylidene group, N value is the integer of 4 to 8.
Wherein, described polymeric alcohol is any one in polyethylene glycol 200, PEG400, Macrogol 600, polypropylene glycol 200, polypropylene glycol 400 and polypropylene glycol 600, it is preferable that polyethylene glycol 200, PEG400 and Macrogol 600.
The preparation method that the present invention is directed to this drilling fluid ether amines composite inhibitor, comprises the following steps:
(1) potassium chloride of described parts by weight is added in the water of described parts by weight, be stirred at room temperature or circulate 15～25 minutes;
(2) ending amino polyether of described parts by weight is added in the mixture that step (1) obtains, be stirred at room temperature or circulate 20～30 minutes;
(3) mixture step (2) obtained adds in the polymeric alcohol of described parts by weight, and temperature 25～40 DEG C obtains this product after stirring or circulating 30～90 minutes.
Wherein, described step (1), (2), stirring in (3) or circulation time preferably 15 minutes, 25 minutes, 60 minutes respectively.
Wherein, the temperature in described step (3) preferably 40 DEG C.
The composite inhibitor another kind scheme of the present invention can also include the Span80 of 2～10 weight portions.
Correspondingly, this drilling fluid preparation method of ether amines composite inhibitor, comprise the following steps:
(1) potassium chloride of described parts by weight is added in the water of described parts by weight, be stirred at room temperature or circulate 15～25 minutes;
(2) ending amino polyether of described parts by weight is added in the mixture that step (1) obtains, be stirred at room temperature or circulate 20～30 minutes;
(3) being added by the Span80 of described parts by weight in the polymeric alcohol of described parts by weight, temperature 25～40 DEG C stirs or circulates 10～30 minutes;
(4) mixture step (2) obtained adds in the mixture that step (3) obtains, and temperature 25～40 DEG C obtains this product after stirring or circulating 30～90 minutes.
Wherein, described step (1), (2), (3), stirring in (4) or circulation time preferably 15 minutes, 25 minutes, 30 minutes, 60 minutes respectively.
Wherein, described step (3), temperature in (4) preferably 25 DEG C, 40 DEG C respectively.
When inhibitor of the present invention is used as drilling fluid shale control agent, it uses temperature to be 5 DEG C～140 DEG C.
The present invention compared with prior art has the advantage that and can ensure on the basis of strong rejection capability by composite this drilling fluid ether amines composite inhibitor obtained of the components such as polyetheramine, it is substantially reduced the blistering rate of organic amine inhibitors, facilitate Field Force's operation to a great extent and control, and reduce froth breaking working time and cost. This ether amines composite inhibitor has higher adaptability, and drilling fluid rheology is little and good with various additive for drilling fluid compatibilities with filtration property impact.
Detailed description of the invention
Below by specific embodiment, technical scheme is further described.
Example 1
Ether amines composite inhibitor includes the component of following weight proportion: polyoxyethylene ether diamine (H2N―R―(OR1)N―NH2, wherein R and R1Being all the alkylidene group with 3 carbon atoms, N value is 6) 60 grams, Polyethylene Glycol (PEG400) 50 grams, 10 grams of potassium chloride, 40 grams of water. Drilling fluid ether amines composite inhibitor is prepared according to the following step:
(1) being dissolved in 40 grams of water by 10 grams of potassium chloride, room temperature 2000rpm rotating speed stirs 15 minutes;
(2) adding in the mixture that step (1) obtains by 60 grams of polyoxyethylene ether diamines, room temperature 2000rpm rotating speed stirs 20 minutes;
(3) mixture step (2) obtained adds in 50 grams of PEG400s, temperature 25 DEG C, and 2000rpm rotating speed obtains product after stirring 30 minutes.
Example 2
Ether amines composite inhibitor includes the component of following weight proportion: polyoxyethylene ether diamine (H2N―R―(OR1)N―NH2, wherein R and R1Being all the alkylidene group with 4 carbon atoms, N value is 4) 150 grams, Polyethylene Glycol (PEG600) 80 grams, sodium formate 30 grams, 160 grams of water. Drilling fluid ether amines composite inhibitor is prepared according to the following step:
(1) being dissolved in 160 grams of water by 30 grams of sodium formates, room temperature 2000rpm rotating speed stirs 20 minutes;
(2) adding in the mixture that step (1) obtains by 150 grams of polyoxyethylene ether diamines, room temperature 2000rpm rotating speed stirs 25 minutes;
(3) mixture step (2) obtained adds in 80 grams of Macrogol 600s, temperature 40 DEG C, and 2000rpm rotating speed obtains product after stirring 60 minutes.
Example 3
Ether amines composite inhibitor includes the component of following weight proportion: polyoxyethylene ether diamine (H2N―R―(OR1)N―NH2, wherein R and R1Being all the alkylidene group with 6 carbon atoms, N value is 8) 1000 grams, Polyethylene Glycol (PEG200) 800 grams, 250 grams of potassium chloride, Span8040 gram, 1000 grams of water. Drilling fluid ether amines composite inhibitor is prepared according to the following step:
(1) being dissolved in 1000 grams of water by 250 grams of potassium chloride, room temperature 2000rpm rotating speed stirs 25 minutes;
(2) adding in the mixture that step (1) obtains by 1000 grams of polyoxyethylene ether diamines, room temperature 2000rpm rotating speed stirs 30 minutes;
(3) 40 grams of Span80 are added in 800 grams of polyethylene glycol 200s, temperature 40 DEG C, 2000rpm rotating speed stirs 30 minutes;
(4) mixture step (2) obtained adds in the mixture that step (3) obtains, temperature 30 DEG C, and 2000rpm rotating speed obtains product after stirring 90 minutes.
The product evaluation of embodiment
The concrete method of testing of drilling fluid is shown in GB/T16783.1-2006, wherein AV, PV, YP, Gel, FL respectively drilling fluid apparent viscosity, plastic viscosity, yield value, gel strength and normal temperature and pressure filter loss, R1, R2 represent shale respectively and once roll the response rate with secondary, and FR is blistering rate; Reference examples be the firm grade of China University Of Petroleum Beijing's clock Chinese (Qiu Zhengsong, Zhong Hanyi, Huang Weian. Novel Polyamine shale control agent characteristic and the mechanism of action [J]. petroleum journal, 2011,32 (4): 678-682.) researched and developed ether amines inhibitor sample; Base slurry concentration and each inorganic agent dosage are quality percentage by volume; " " expression is not surveyed.
(1) mud yield is suppressed
Test preparation is starched, and adds 350 ml distilled waters, 3.5 grams of samples, after fully dissolving, adds 35.0 grams of sodium bentonites, stirring 20 minutes on high speed agitator, and curing in airtight condition is after 24 hours, and high-speed stirred 5 minutes measures its apparent viscosity AV immediately; Preparing 10% base to starch as reference, curing in airtight condition measures its apparent viscosity AV after 24 hours0, then mud yield MR=(AV is suppressed0-AV)/AV0× 100. Same method is used to measure the suppression mud yield after rolling 16 hours at 120 DEG C. 10% base slurry apparent viscosity respectively 30mPa.s and 48mPa.s after room temperature and heat are rolled.
As shown in Table 1, products obtained therefrom of the present invention suppresses mud yield higher, it is possible to effectively suppresses shale hydration to expand, has good rejection ability.
The rejection ability of table 1 organic amine inhibitors, foamability and to base starch performance impact evaluation
(2) shale rolls the response rate
Shale rolls recovery test method to carry out according to mud shale distributed test method in SY/T5613-2000 " mud shale physicochemical property test method ", landwaste takes from the blue or green Dong34Jing of triumph, sample solution is prepared according to mass percent 1.0%, rolls taking-up in 16 hours and carry out subsequent step at 120 DEG C;And measure secondary and roll the response rate, the landwaste being about to once roll recovery again rolls in distilled water, and replication obtains second heat and rolls back yield. Landwaste once rolls the response rate respectively 21.26% and 8.55% with secondary in distilled water. As shown in Table 1, products obtained therefrom of the present invention has significantly high shale and rolls the response rate, and its secondary rolling response rate is higher, illustrates that its rejection ability has long-lasting.
(3) blistering rate
In measuring according to suppressing mud yield, method test preparation slurry 350mL, high-speed stirred 5 minutes under 6000r/min, pour in 1000 milliliters of graduated cylinders immediately, starts timing, reads experiment volume of slurry V after standing 10 seconds. Then blistering rate FR=(V-350)/350 × 100. As shown in Table 1, comparing reference examples ether amines inhibitor product, products obtained therefrom blistering rate of the present invention is extremely low, just produces almost without bubble when adding drilling fluid; Comparing to after reference examples ether amines inhibitor adds and bubble in a large number, all cannot eliminate the situation of bubble after even circulating/roll a period of time, product of the present invention has clear superiority.
(4) heat-resisting property
Investigating different temperatures heat and roll the suppression mud yield of rear sample, as can be seen from Table 2, products obtained therefrom temperature resistance of the present invention reaches 140 DEG C; Due to the phenomenon having crystal to precipitate out in system when observing lower than 5 DEG C, when therefore inhibitor of the present invention is used as drilling fluid shale control agent, it uses temperature to be 5 DEG C～140 DEG C.
The temperature resistance merit rating of table 2 organic amine inhibitors
(5) impact of performance starched by base by sample
Preparation mass volume ratio is 350 milliliters of the base slurry of 6%, and curing in airtight condition adds 1.75 grams of samples after 24 hours, measure its apparent viscosity AV after rolling 16 hours at 120 DEG C1And API filtration FL1; Base slurry is carried out heat equally and rolls and measure its apparent viscosity AV0And API filtration FL0, then apparent viscosity rate of change AVR=(AV after base slurry addition sample1-AV0)/AV0× 100, filter loss rate of change FLR=(FL1-FL0)/FL0× 100. As shown in Table 1, its stream is become suitable with reference examples ether amines inhibitor product with the impact of filtration property after adding base slurry by products obtained therefrom of the present invention.
(6) compatibility test
Based on the conventional aqueous-based polymers drilling fluid composition in scene (each inorganic agent dosage is quality percentage by volume): 5% bentonite+0.3% soda+0.2% Caustic soda+0.1%PAM+0.3% ammonium salt+0.5%LV-CMC+0.3%KPAM+3% polymeric alcohol+2%SD201+3%SMP-2, it is designated as 1# slurry, starch at 1# and basis adds 1.0% sample, measure its stream after rolling 16 hours in 120 DEG C to become and filtration property, investigate the organic amine inhibitors impact on drilling fluid. As shown in Table 3, its stream is become less with the impact of filtration property after adding test slurry by products obtained therefrom of the present invention, good with conventional water-base drilling fluid inorganic agent compatibility.
Table 3 organic amine inhibitors compatibility is tested
(7) blue or green eastern 34 well scene tests
Blue or green eastern 34 well locations, in 34 pieces of higher part positions, Jiyang depression Qingdong sag the north step-fault zone green grass or young crops east, design well depth 3700 meters, and main purpose layer is SHAHEJIE FORMATION (dune shape), holds concurrently and visits the Mesozoic group, Archaean group, finishing drilling layer position; Main layer lithology is Lycoperdon polymorphum Vitt mud stone is main, presss from both sides Lycoperdon polymorphum Vitt Sandy Silt, argillaceous siltstoue; Target zone is LOW PERMEABILITY RESERVOIR, permeability 0.85～5.1 millidarcy.
This well drilling fluid composition: base slurry+0.3～0.5%IND30+0.5～aluminium base polymer of 1.0%NAT20+2～3%SMP-2+2～3% nanoemulsions+0.5～1% polymeric alcohol+0.3～0.5%, the ether amines composite inhibitor of 1.0% is added in 2550m circulation, before and after adding, property of drilling fluid is in Table 4, visible its is little to actual well drilled liquid performance impact after adding, and blistering rate is very low, facilitate on-the-spot application to a great extent.
The blue or green eastern 34 well scene applicable cases of table 4
Claims (9)
1. a drilling fluid ether amines composite inhibitor, is characterized in that including the component of following weight portion, ending amino polyether-60～100 parts, polymeric alcohol-40～80 parts, potassium chloride or sodium formate, potassium formate-10～25 parts ,-40～100 parts of water.
2. drilling fluid ether amines composite inhibitor according to claim 1, is characterized in that: described ending amino polyether is general molecular formula is H2N―R―(OR1)N―NH2Polyoxyethylene ether diamine, R and R in general molecular formula1Being have 3 to 6 different carbon atom numbers or same carbon atoms number purpose alkylidene group, N value is the integer of 4 to 8.
3. drilling fluid ether amines composite inhibitor according to claim 2, is characterized in that: described polymeric alcohol is any one in polyethylene glycol 200, PEG400, Macrogol 600, polypropylene glycol 200, polypropylene glycol 400 and polypropylene glycol 600.
4. drilling fluid ether amines composite inhibitor according to claim 3, is characterized in that: any one of the preferred polyethylene glycol 200 of described polymeric alcohol, PEG400 or Macrogol 600.
5. the ether amines composite inhibitor of the drilling fluid according to any one of claim 1-4, is characterized in that: also include the Span80 of 2～10 weight portions in described component.
6. the preparation method of ether amines composite inhibitor of the drilling fluid according to any one of claim 1-4, is characterized in that comprising the following steps:
(1) potassium chloride of described parts by weight is added in the water of described parts by weight, be stirred at room temperature or circulate 15～25 minutes;
(2) ending amino polyether of described parts by weight is added in the mixture that step (1) obtains, be stirred at room temperature or circulate 20～30 minutes;
(3) mixture step (2) obtained adds in the polymeric alcohol of described parts by weight, and temperature 25～40 DEG C obtains this product after stirring or circulating 30～90 minutes.
7. the preparation method of ether amines composite inhibitor of the drilling fluid described in claim 5, is characterized in that comprising the following steps:
(1) potassium chloride of described parts by weight is added in the water of described parts by weight, be stirred at room temperature or circulate 15～25 minutes;
(2) ending amino polyether of described parts by weight is added in the mixture that step (1) obtains, be stirred at room temperature or circulate 20～30 minutes;
(3) being added by the Span80 of described parts by weight in the polymeric alcohol of described parts by weight, temperature 25～40 DEG C stirs or circulates 10～30 minutes;
(4) mixture step (2) obtained adds in the mixture that step (3) obtains, and temperature 25～40 DEG C obtains this product after stirring or circulating 30～90 minutes.
8. the preparation method of drilling fluid ether amines composite inhibitor according to claim 6, is characterized in that: stirring or circulation time in described step (1), (2), (3) distinguish preferably 15 minutes, 25 minutes, 60 minutes; Temperature in step (3) preferably 40 DEG C.
9. the preparation method of drilling fluid ether amines composite inhibitor according to claim 7, is characterized in that: stirring or circulation time in described step (1), (2), (3), (4) distinguish preferably 15 minutes, 25 minutes, 30 minutes, 60 minutes; Temperature difference preferably 25 DEG C, 40 DEG C in step (3), (4).
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| CN111826137A (en) * | 2019-04-15 | 2020-10-27 | 中石化石油工程技术服务有限公司 | Amino polyether drilling fluid and preparation method thereof |
| WO2021128745A1 (en) * | 2019-12-24 | 2021-07-01 | 中国海洋石油集团有限公司 | Oil-based drilling fluid and preparation method therefor, and preparation method for anti-settling stabilizer |
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Application publication date: 20160615 |