CN111676003A - Environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor - Google Patents
Environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor Download PDFInfo
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Abstract
The low molecular weight polyether ammonia is synthesized by using ester compounds with amino groups and ether bonds and ether compounds containing olefinic bonds as raw materials by a one-pot synthesis method or a step synthesis method. The shale intercalation inhibitor prepared from the low-molecular-weight branched polyether ammonia is prepared by mixing the low-molecular-weight branched polyether ammonia with water, wherein the mass ratio of the low-molecular-weight branched polyether ammonia in the shale intercalation inhibitor is 0.5-3%. The shale intercalation inhibitor prepared from the low-molecular-weight branched polyether ammonia has good biodegradability, is safe and nontoxic, has obviously improved inhibition performance compared with similar intercalation inhibitors, is easy to obtain raw materials and low in price, and the provided synthesis method is stable and reliable and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of oil and gas field drilling, in particular to a low-molecular-weight branched polyether ammonia shale intercalation inhibitor.
Background
Borehole wall instability has always been a worldwide problem to be overcome during drilling. It often results in complex accidents such as borehole wall collapse, hole shrinkage, stuck drill, etc., increasing drilling time and drilling cost. According to statistical data, 75% of the borehole wall instability problems mainly occur in shale formations, particularly water-sensitive formations, the shale formations have high clay mineral content, the horizontal sections of shale gas horizontal wells are long, the drilling fluid is in contact with the formations for a long time, the shale is more seriously hydrated, and the borehole wall instability is more prominent. Although the oil-based drilling fluid has the advantages of high temperature resistance, salt and calcium corrosion resistance, contribution to well wall stability, good lubricity, small damage degree to an oil-gas layer and the like, the preparation cost of the oil-based drilling fluid is much higher than that of the water-based drilling fluid, the oil-based drilling fluid often causes serious influence on the ecological environment nearby a well site when in use, the mechanical drilling speed is generally lower than that of the water-based drilling fluid, and the popularization and the application of the oil-based drilling fluid are greatly limited by the defects.
With the gradual improvement of the environmental protection requirement in recent years, the development of water-based drilling fluid which has the same effect as oil-based drilling fluid and meets the environmental protection requirement to replace the oil-based drilling fluid is a trend of the current drilling fluid technology development. In order to overcome the defects of the existing inhibitor, researchers have conducted a great deal of experimental research on the inhibitor, but the variety really accepted by the market is not many, and particularly, the water-based drilling fluid which is suitable for high temperature and high density and meets the environmental protection requirement is still to be developed. In recent years, ether substances have attracted attention because of their advantages such as no biological toxicity, safety, and degradability.
The polyamine inhibitors studied and applied at present are mostly linear structures, and for the linear polyamine inhibitors, the linear polyamine inhibitors usually have irregular linear configurations after being dissolved in water, and when the linear polyamine inhibitors are used in a shale gas drilling process, winding and coating on clay are uneven, so that repeated adsorption or no adsorption is easily caused. Meanwhile, the acting groups are generally arranged at two ends of a molecular chain, so that one molecular chain generally only contains two acting groups, the acting effect of the linear polyether ammonia inhibitor is limited in this case, and the polyamine compound with high molecular weight is difficult to enter between clay layers, so that the inhibiting performance of the polyamine is limited.
Disclosure of Invention
Aiming at the defects of the existing shale intercalation inhibitor, the invention provides the shale intercalation inhibitor prepared from the environment-friendly branched polyether ammonia in view of the problems, the inhibitor responds to the environment-friendly requirement, the inhibition performance is obviously improved compared with similar products, the drilling requirements of various complex well conditions can be completely met, the synthesis process is simple and environment-friendly, the yield is higher, the production cost is low, and the shale intercalation inhibitor is suitable for industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows: the shale intercalation inhibitor is prepared by mixing low-molecular-weight branched polyether ammonia and water, wherein the mass ratio of the low-molecular-weight branched polyether ammonia is 0.5-3%, the low-molecular-weight branched polyether ammonia is synthesized by taking ester compounds with amino groups and ether bonds and ether compounds containing olefinic bonds as raw materials through a one-pot synthesis method or a distributed synthesis method.
The one-pot synthesis method comprises the following operation steps: respectively dissolving 0.1mol of ester compound with amino and ether bond (wherein the number of the amino groups is m) and 0.1m mol of ether compound containing olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution containing olefinic bond into the ester compound solution with amino and ether bond under stirring at 25-35 deg.C under nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G3 low-molecular-weight branched polyether ammonia.
The step-by-step synthesis method comprises the following operation steps:
s1, respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1mol of ether compound with olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution with olefinic bond into the ester compound solution with amino and ether bond under the condition of stirring at 25-35 ℃ in nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G1 low-molecular-weight branched polyether ammonia.
S2, respectively dissolving the G1 low molecular weight branched polyether ammonia obtained in S1 and 0.1mol of ether compound containing olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution containing olefinic bond into the ester compound solution containing amino and ether bond under the condition of stirring at 25-35 ℃ in nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G2 low-molecular-weight branched polyether ammonia.
S3, reacting the G2 low molecular weight branched polyether ammonia obtained in the S2 according to the step S2, wherein the maximum reaction step number of the reaction steps is m of hydrogen atoms of amino groups contained in ester compounds with amino groups and ether bonds, and obtaining the corresponding G1-Gm low molecular weight branched polyether ammonia after the reaction of the steps is finished.
The ester compound having an amino group and an ether bond is N- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- (2-aminoethoxy) ethyl ] ethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -1-methylethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] propyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -2-methylpropyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methylethyl ethoxy carbamate, 5,8, 11-trioxo-2-azadecanoic acid-1, 3-amino-1, 1-dimethylethyl ester, 5,8,11, 14-tetraoxy-2-azahexadecanoic acid-16-amino-1, 1-dimethylethyl ester, 5,8,11,14, 17-pentoxy-2-azaazelaic acid-19-nitrogen-1, 1-dimethylethyl ester, and an alkene compound containing an ether bond is one of vinyl n-butyl ether, vinyl isobutyl ether, 2-ethylhexyl vinyl ether, 2-methoxyethyl vinyl ether and 2- [ (2-methoxy) ethoxy ] ethyl ether.
The titration time of the dripping step is controlled to be 25-35 min.
The rotary evaporation temperature is 65 ℃, and the absolute vacuum degree is less than 3000 Pa.
The invention has the following beneficial effects:
1. the product designed by the invention responds to the requirement of environmental protection, has the advantages of no biological toxicity, safety and easy degradation, and belongs to an environment-friendly inhibitor;
2. the synthesis method has stable and reliable technology, high yield and low price of raw materials required by the synthesized product, and is suitable for industrial production;
3. the shale inhibitor provided by the invention is a low molecular weight branched polyetheramine shale intercalation inhibitor, has stable performance and strong adaptability, has obviously improved inhibition performance compared with similar products, and can meet the drilling requirements of various complex well conditions.
Drawings
FIG. 1 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether ammonia in example 1;
FIG. 2 is a graph showing the distribution of the molecular weight of G1 low molecular weight branched polyether ammonia in example 2;
FIG. 3 is a graph showing the distribution of the molecular weight of G2 low molecular weight branched polyether ammonia in example 2;
FIG. 4 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether amine in example 2;
FIG. 5 is a graph showing the distribution of the molecular weight of G1 low molecular weight branched polyether amine in example 3;
FIG. 6 is a graph showing the distribution of the molecular weight of G2 low molecular weight branched polyether amine in example 3;
FIG. 7 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether ammonia in example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the preparation method of the low molecular weight branched polyether ammonia by using carbamic acid N- [2- (2-aminoethoxy) ethyl ] methyl ester and vinyl isobutyl ether as raw materials and adopting a one-pot method comprises the following specific operation steps:
0.1mol of N- [2- (2-aminoethoxy) ethyl ] methyl carbamate and 0.3mol of vinyl isobutyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is as follows:
example 2:
the branched polyether ammonia with low molecular weight is prepared by a fractional synthesis method by taking carbamic acid N- [2- (2-aminoethoxy) ethyl ] methyl ester and vinyl isobutyl ether as raw materials, and the specific operation steps are as follows:
0.1mol of N- [2- (2-aminoethoxy) ethyl ] methyl carbamate and 0.1mol of vinyl isobutyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G1 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G1 low molecular weight branched polyetheramine and 0.1mol of vinyl isobutyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the completion of the dropwise addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G2 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G2 low molecular weight branched polyetheramine and 0.1mol of vinyl isobutyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is
Example 3:
the low molecular weight branched polyether ammonia is prepared by taking carbamic acid N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl ester and vinyl N-butyl ether as raw materials and adopting a stepwise synthesis method, and the specific operation steps are as follows:
0.1mol of N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl carbamate and 0.1mol of vinyl N-butyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl carbamate was placed in a three-neck flask, and vinyl N-butyl ether was placed in a separatory funnel and added dropwise to the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G1 low-molecular-weight branched polyether ammonia.
The molecular structural formula is
0.1mol of G1 low molecular weight branched polyetheramine and 0.1mol of vinyl n-butyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. G1 low molecular weight branched polyether ammonia was placed in a three-neck flask, and vinyl n-butyl ether was placed in a separatory funnel and added dropwise into the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G2 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G2 low molecular weight branched polyetheramine and 0.1mol of vinyl n-butyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol respectively. G2 low molecular weight branched polyether ammonia was placed in a three-neck flask, and vinyl n-butyl ether was placed in a separatory funnel and added dropwise into the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is
1. Molecular weight measurement
The hyperbranched polyguanylic acid contained in the examples was subjected to a molecular weight test using TOF-LC/MS, and the test results are shown in FIGS. 1 and 2. According to the results of polymer mass spectrum tests, G3 low molecular weight branched polyether ammonia obtained in example 1 shows peaks at positions 366.396, 367.241, 368.024 and 369.712, respectively, which are consistent with theoretical values, and G2 low molecular weight branched polyether ammonia obtained in example 2 shows peaks at positions 307.326, 308.021, 309.413 and 310.502, respectively, which are consistent with theoretical values. Thus demonstrating the success of low molecular weight branched polyether ammonia synthesis.
2. Linear expansion rate test
The low molecular weight branched polyether ammonia obtained in example 1-2 and clean water were prepared in a ratio (the low molecular weight branched polyether ammonia mass ratio was 1%, 2%, 3%) into shale inhibitors and conventional shale inhibitors (conventional polyamine inhibitors and hexamethylenediamine inhibitors were selected) for comparative experiments, and clean water was used as a reference. The inhibition performance prepared in the above examples is evaluated by adopting a linear expansion ratio, and the specific operation steps refer to the petroleum and natural gas industry standard SY/T6335-1997 evaluation method of shale inhibitors for drilling fluids. The lower the linear expansion ratio, the better the inhibition performance of the inhibitor. The results of the experiments are shown in the following table.
TABLE 1 Effect of different intercalation inhibitors on Linear expansion Rate
TABLE 2 Effect of intercalation inhibitor addition on Linear expansion Rate
The results of the influence of different intercalation inhibitors on the linear expansion rate in table 1 show that when ethylenediamine, polyamine and the low molecular weight branched polyether ammonia obtained in different examples are in the same proportion, the inhibition performance of the low molecular weight branched polyether ammonia is obviously higher than that of the conventional shale inhibitors such as hexamethylenediamine and polyamine. The inhibition effect of the low molecular weight branched polyether ammonia shale inhibitor is obviously higher than that of the conventional shale inhibitor. The influence of the inhibitor content on the linear expansion rate shows that the linear expansion rate is reduced along with the increase of the inhibitor addition amount, the inhibition performance is better, and when the inhibitor addition amount reaches 4%, the inhibition effect reaches a peak value.
3. Environmental protection test
The low molecular weight branched polyether ammonia serving as the shale intercalation inhibitor has the advantages of excellent inhibition performance, simple production process and easy biodegradation. The international Organization for Economic Cooperation and Development (OECD) issued a series of standards on biodegradability of chemicals, which have become an important basis for environmental hazard assessment and risk assessment of chemicals, wherein the OECD301 series of standards specifies 6 chemical rapid biodegradation test methods, according to which test methods can be considered as biodegradable substances. According to the test standard of the sealed bottle method (301D), when the biodegradation rate (BOD/COD) of the chemical is 28 days, the biodegradation rate BOD/COD is not less than 60%, and it can be considered that the chemical is easily biodegraded.
The biodegradability (BOD5/CODcr) is used herein to represent the biodegradability, BOD5 (reference standard HJ/T505-2009) is determined by inoculation and dilution methods, CODcr (reference standard YJ/T377-2007) is determined by potassium dichromate method, BOD5/CODcr is respectively measured for G3 low molecular weight branched polyether ammonia in example 1, G1 low molecular weight branched polyether ammonia in example 2, G2 in example 2, G3 in example 2, example 3G1, example 3G2, and example 3G3, and the final results are respectively 61.2%, 64.8%, 63.2%, 61.4%, 64.3%, 62.7%, 60.9%, thus the product can reach the OECD environmental protection standard and is easily degraded compared with hexamethylenediamine, which is a commonly used inhibitor in the art, and the BOD of the product is easily degraded5The ratio of/CODcr is 1%, which is much lower than the normal index, indicating poor biodegradability. Indicating that the product is an environmentThe shale inhibitor is friendly, and the environmental protection performance is obviously improved compared with the conventional inhibitor.
In conclusion, the preparation method of the low molecular weight branched polyether ammonia provided by the invention has the advantages of stable and reliable technology and high yield, and is suitable for industrial production; the synthesized low molecular weight branched polyether ammonia product is non-toxic and harmless, has good water solubility, and the inhibition performance of the prepared shale intercalation inhibitor is obviously improved compared with similar products, thereby meeting the drilling requirements of various complex well conditions and effectively reducing the occurrence probability of unstable well wall caused by shale hydration dispersion.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor is characterized in that the shale intercalation inhibitor is prepared by mixing low-molecular-weight branched polyether ammonia and water, wherein the mass ratio of the low-molecular-weight branched polyether ammonia is 0.5-3%, and the low-molecular-weight polyether ammonia is synthesized by using an ester compound with amino and ether bonds and an ether compound with olefinic bonds as raw materials through a one-pot synthesis method or a step synthesis method.
2. The inhibitor according to claim 1, wherein the ester compound having an amino group and an ether bond is N- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- (2-aminoethoxy) ethyl ] ethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -1-methylethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] propyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -2-methylpropyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methylethyl ethoxy carbamate, 5,8, 11-trioxa-2-aza decanoic acid-1, 3-amino-1, 1-dimethyl ethyl ester, 5,8,11, 14-tetraoxy-2-aza hexadecanoic acid-16-amino-1, 1-dimethyl ethyl ester, 5,8,11,14, 17-pentoxy-2 aza azelaic acid-19-nitrogen radical-1, 1-dimethyl ethyl ester.
3. The inhibitor according to claim 1, wherein the vinyl compound containing an ether bond is one of vinyl n-butyl ether, vinyl isobutyl ether, 2-ethylhexyl vinyl ether, 2-methoxyethyl vinyl ether, and 2- [ (2-methoxy) ethoxy ] ethyl ether.
4. The inhibitor according to claim 1, wherein the one-pot synthesis comprises the following steps:
respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1m mol of ether compound with olefin bond in 80-100ml of equivalent solvent, wherein m is the number of amino groups contained in the ester compound with amino and ether bond, dripping the ether compound solution with olefin bond into the ester compound solution with amino and ether bond under the conditions of 25-35 ℃ temperature, nitrogen atmosphere and stirring, completing titration, heating to 65-85 ℃, carrying out reflux reaction for 4-10h, and carrying out rotary evaporation after the reaction is completed to obtain the Gm low molecular weight branched polyether ammonia.
5. The inhibitor according to claim 1, characterized in that the distributed synthesis method comprises the following steps:
s1, respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1mol of ether compound with olefinic bond in 80-100ml of equivalent solvent, dropwise adding the ether compound solution with olefinic bond into the ester compound solution with amino and ether bond under the conditions of 25-35 ℃ and nitrogen stirring, raising the temperature to 65-85 ℃ after titration, carrying out reflux reaction for 4-10h, and carrying out rotary evaporation after the reaction is finished to obtain G1 low-molecular-weight branched polyether ammonia;
s2, taking the product obtained in the previous step and the ether compound containing the olefinic bond with the same molar weight as the product, repeating the step S1 m times, wherein m is the number of amino groups of the ester compound with amino and ether bonds used in the step S1, and the product obtained in each step is G1-Gm low molecular weight branched polyetheramine.
6. The shale intercalation inhibitor made of low molecular weight branched polyether ammonia according to claims 3-4, wherein the solvent is one of absolute methanol, absolute ethanol, tetrahydrofuran, DMSO, DMF.
7. The shale intercalation inhibitor made of environment-friendly low molecular weight branched polyether ammonia as claimed in claims 3-4, wherein the dropping time is controlled within 25-35 min.
8. The shale intercalation inhibitor made of environment-friendly low-molecular-weight branched polyether ammonia as claimed in claims 3-4, wherein the rotary evaporation temperature is 65 ℃ and the absolute vacuum degree is less than 3000 Pa.
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| CN113416525A (en) * | 2021-06-22 | 2021-09-21 | 西南石油大学 | Environment-friendly polyether tertiary amine as shale surface hydration inhibitor |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4757862A (en) * | 1986-08-21 | 1988-07-19 | Petrolite Corporation | Shale stabilizer and method of use thereof |
| CN1140743A (en) * | 1996-04-06 | 1997-01-22 | 温固 | Collapse-preventing lubricator for inhibiting hydration expansion of clay |
| GB0424768D0 (en) * | 2004-11-10 | 2004-12-08 | Ciba Spec Chem Water Treat Ltd | Inhibition of clay or shale |
| CN1882623A (en) * | 2003-11-21 | 2006-12-20 | 巴斯福股份公司 | Copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms |
| WO2014191389A1 (en) * | 2013-05-29 | 2014-12-04 | Lamberti Spa | Shale inhibitors |
| US20150344767A1 (en) * | 2012-12-05 | 2015-12-03 | Isp Investments Inc. | Shale swelling inhibitors |
| CN105255460A (en) * | 2015-10-29 | 2016-01-20 | 中石化江汉石油工程有限公司 | Water-based drilling fluid suitable for shale gas development |
| CN107573911A (en) * | 2017-09-20 | 2018-01-12 | 中国石油集团渤海钻探工程有限公司 | A kind of high performance water-based drilling fluid formula |
| CN109777377A (en) * | 2019-02-12 | 2019-05-21 | 西南石油大学 | Shale intercalation inhibitor made of a kind of Ultra-low molecular weight branching tertiary amine-type polyamine |
| CN111117580A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Strong-adsorption amino inhibitor for drilling fluid and preparation method thereof |
| CN113429579A (en) * | 2021-06-22 | 2021-09-24 | 西南石油大学 | Strong-adsorption branched tertiary amine silanol serving as shale surface hydration inhibitor |
-
2020
- 2020-07-22 CN CN202010710424.2A patent/CN111676003B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4757862A (en) * | 1986-08-21 | 1988-07-19 | Petrolite Corporation | Shale stabilizer and method of use thereof |
| CN1140743A (en) * | 1996-04-06 | 1997-01-22 | 温固 | Collapse-preventing lubricator for inhibiting hydration expansion of clay |
| CN1882623A (en) * | 2003-11-21 | 2006-12-20 | 巴斯福股份公司 | Copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms |
| GB0424768D0 (en) * | 2004-11-10 | 2004-12-08 | Ciba Spec Chem Water Treat Ltd | Inhibition of clay or shale |
| US20150344767A1 (en) * | 2012-12-05 | 2015-12-03 | Isp Investments Inc. | Shale swelling inhibitors |
| WO2014191389A1 (en) * | 2013-05-29 | 2014-12-04 | Lamberti Spa | Shale inhibitors |
| CN105255460A (en) * | 2015-10-29 | 2016-01-20 | 中石化江汉石油工程有限公司 | Water-based drilling fluid suitable for shale gas development |
| CN107573911A (en) * | 2017-09-20 | 2018-01-12 | 中国石油集团渤海钻探工程有限公司 | A kind of high performance water-based drilling fluid formula |
| CN111117580A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Strong-adsorption amino inhibitor for drilling fluid and preparation method thereof |
| CN109777377A (en) * | 2019-02-12 | 2019-05-21 | 西南石油大学 | Shale intercalation inhibitor made of a kind of Ultra-low molecular weight branching tertiary amine-type polyamine |
| CN113429579A (en) * | 2021-06-22 | 2021-09-24 | 西南石油大学 | Strong-adsorption branched tertiary amine silanol serving as shale surface hydration inhibitor |
Non-Patent Citations (4)
| Title |
|---|
| REN YJ: "amine- and alcohol- functionalized ionic liquids: inhibition difference and application in water-based drilling fluids for wellbore stability", 《COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
| 张卫东: "页岩抑制剂的抑制机理及研究进展", 《钻井液与完井液》 * |
| 都伟超: "黏土水化抑制剂Gemini-DHEDB和PDWC的合成及作用机理研究", 《中国博士学位论文全文数据库》 * |
| 魏云锦: "超支化聚合物HP-NH2的合成及防塌机理研究", 《西南石油大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416525A (en) * | 2021-06-22 | 2021-09-21 | 西南石油大学 | Environment-friendly polyether tertiary amine as shale surface hydration inhibitor |
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