CN106281263B - A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof - Google Patents
A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof, including following ingredient：Any one or a few in ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, five ethamine of diethylenetriamine, it is formulated according to 0.5~3% ratio and clear water, the ammonia triethylamine is synthesized by nitrilotriacetic acid, the Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediamine tetra-acetic acid, five ethamine of the diethylenetriamine is synthesized by diethylene triamine pentacetic acid (DTPA), is added raw materials into absolute ethyl alcohol, is reacted after the concentrated sulfuric acid is added, it adds organic solvent and is passed through ammonium hydroxide, product is made in stirring distillation.The method can significantly improve the rejections of drilling fluid system, and heatproof reaches 240 DEG C or more, fully meet the demand of ultra-deep well drilling, effectively reduce the problem of due to shale hydration disperseing that hole instability occurs, and synthesis technology is simple and environmentally-friendly, yield is higher, low production cost, is suitble to industrialized production.
Description
Technical field
The invention belongs to oilfield drilling technical fields, and in particular to a kind of to be suitable for boring shale gas horizontal well horizontal segment
Water-base drilling fluid inhibitor and preparation method thereof.
Background technology
At present at home in external drilling well, it is frequently present of borehole instability problems.Hole instability may result in well
The problems such as wall caves in, undergauge, bit freezing, increases drilling time and drilling cost.75% hole instability occurs mainly in mud
Shale formation, especially water-sensitive strata.
China's shale gas resources exploration has been in full swing, and for the accumulation feature of shale gas, horizontal well has become page
The main drilling mode of rock gas exploitation.Compared with conventional horizontal well, shale horizontal well horizontal segment is longer, it is typically in the range of 500~
2500m, the time that drilling fluid is contacted with stratum increase, and Shale Hydration is more serious.Drilling fluid filtrate enters stratification gap, shale
Interior clay mineral water-swellable, the bulbs of pressure make tension increase, and lead to shale formation (part) tensile fracture, the borehole wall occur and collapse
It collapses, the down hole problems such as undergauge.60%~70% external shale gas horizontal well uses oil base drilling fluid system, the country to complete
The shale gas horizontal well overwhelming majority use oil base drilling fluid system, oil base drilling fluid has that borehole wall stability is good, rejection ability
By force, lubricity is good, the advantages of being conducive to protect reservoir, but exist not environmentally, the shortcomings of the cost is relatively high.Water-base drilling fluid
Just the shortcomings that capable of overcoming oil base drilling fluid, but water-base drilling fluid at this stage is steady to mud stone or the strong retraction shale formation borehole wall
Fixed aspect still has problem, needs targetedly to further investigate.
Mainly use inorganic salts as inhibitor on oil field at this stage, but the inorganic salts of high concentration not only seriously affect
The rheological characteristic of drilling fluid, and serious pollution is caused to underground environment.Conventional shale control agent is containing there are two primary amine groups
Group or polyetheramine, kiber alkyl amine seriously affect the rheological characteristic and dehydration wave making machine of drilling fluid, and alkyl two as inhibitor
Being more toxic for amine, does not meet environmental requirement.The shale control agent of polyamine class often increases in carbochain to increase its water solubility
Add hydroxyl and ehter bond, but this also reduces its rejection, and temperature resistance ability is limited.
With the development of ultradeep well exploration and development, to the research and development of shale control agent, more stringent requirements are proposed.Due to the use of
Water base drilling fluid system bores shale gas horizontal well, and water is contacted with stratum at first, leads to the clay hydration swelling on stratum, in order to inhibit
The hydration swelling of clay, shale control agent must be rapidly inserted into clay interlayer, squeeze out the hydrone of clay interlayer, reduce interlayer
Away from.The study found that increasing with primary amine group quantity, adsorption rate of the inhibitor on clay is accelerated.
Invention content
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of suppressions for the low molecular weight carrying 3~5 primary amine groups
Preparation and preparation method thereof, it can not only significantly improve the rejection of drilling fluid system, and heatproof reaches 240 DEG C or more, complete
The demand of full up foot ultra-deep well drilling, effectively reduces the problem of due to shale hydration disperseing that hole instability occurs.And it synthesizes
Simple for process, environmentally friendly, yield is higher, low production cost, is suitble to industrialized production.
Technical scheme is as follows：
A kind of Ultra-low molecular weight intercalation inhibitor, by ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, five ethamine of diethylenetriamine
Any one or a few is mixed into 0.5~3% weight ratio, remaining is water；
The structural formula of the ammonia triethylamine is：
The structural formula of the Ethylenedinitrilotetraacetic Acid is：
The structural formula of five ethamine of the diethylenetriamine is：
Further, the ammonia triethylamine is synthesized by nitrilotriacetic acid, and the structural formula of nitrilotriacetic acid is：
The Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediamine tetra-acetic acid, and the structural formula of ethylenediamine tetra-acetic acid is：
Five ethamine of the diethylenetriamine is synthesized by diethylene triamine pentacetic acid (DTPA), the structural formula of diethylene triamine pentacetic acid (DTPA)
For：
The present invention also provides a kind of preparation methods of Ultra-low molecular weight intercalation inhibitor, and steps are as follows：
S1, the raw material of 0.1~0.2mol is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols, adds
Enter 5~10ml concentrated sulfuric acids, 3~5h is reacted at 75~90 DEG C, obtains product；
S2, it after the obtained products of step S1 are cooled to room temperature, is concentrated under reduced pressure, 100ml dichloromethane is added, at 0~5 DEG C
Under the conditions of be added dropwise 10% sodium hydroxide solution, until pH test paper in alkalinity after, detach organic layer, anhydrous magnesium sulfate drying, mistake
Filter, distillation, obtains the product with carboxylic acid, ethyl ester functional group；
The product with carboxylic acid, ethyl ester functional group obtained in S3, step S2, takes 0.05~0.1mol to be dissolved in 50ml organic
In solvent, (equivalent calculates the methanolic ammonia solution of 5~10 equivalents of addition according to number of ester groups amount, such as there are three carboxylic acid groups for nitrilotriacetic acid
Group, there are three ester groups after being esterified, then the ammonia methanol of 5~10 times of an ester group addition, opposite nitrilotriacetic acid need addition 15
~30 times of ammonia methanol), 1~10% sodium methoxide is added, is vigorously stirred under 50 DEG C of water bath conditions for 24 hours, vacuum distillation is removed
Solvent obtains product；
S4, the 0.05~0.1mol products obtained in step S3 are dissolved in organic solvent, under the conditions of 5~10 DEG C,
0.05~0.2mol sodium borohydrides are added, 0.1~0.3mol boron trifluoride ether is added dropwise, or 0.1~0.3mol hydrogenations are added
Aluminium lithium is warming up to room temperature reaction 12h；After completion of the reaction, water is slowly added dropwise to be quenched, then evaporation drying, is slowly added dropwise
The hydrochloric acid solution of 5mol/L drips back flow reaction 1h, evaporation drying after finishing and is dissolved in water residual solid, is added 5mol/L's
Sodium hydroxide solution stirs 30min, and drying solid is dissolved in anhydrous ether, then filters by evaporation drying, rotary evaporation
Fall ether, obtains product；
S5, reaction kettle is added according to required ratio in step S4 resulting products, stirs, is configured to ultralow after clear water is added
Molecular weight intercalation inhibitor.
Raw material described in step S1 is one kind in nitrilotriacetic acid, ethylenediamine tetra-acetic acid, diethylene triamine pentacetic acid (DTPA)；
Organic solvent described in step S3 is tetrahydrofuran, pyridine, n,N-Dimethylformamide, N, N- dimethylacetamides
Amine, one kind in dimethyl sulfoxide；
The step of methanolic ammonia solution being added in step S3, can be replaced and be passed through ammonia or addition ammonium hydroxide.
The advantage of the invention is that：
1, product of the invention, can be rapidly inserted into inside clay crystal layer, branched structure can firmly be adsorbed on clay crystal layer
Surface, squeeze out the absorption water of interlayer, inhibit surface hydration, effectively reduce since shale hydration disperses that hole instability occurs
The problem of, it is suitable for various soft mudstone stratum, saline bed, strong retraction stratum and other bad grounds, ultra-long horizontal well can be met
The use of section environment；
2, hydroxyl and ehter bond are not contained in inhibitor molecules, improve the heat-resisting property of inhibitor, temperature resistance can reach 240
DEG C, the demand of ultra-deep well drilling is fully met, increasing for primary amine group quantity also reduces its bio-toxicity；
3, low in raw material price needed for product, synthesis technology is simple and environmentally-friendly, and yield is higher, is suitble to industrialized production.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, but does not constitute any limit to the present invention
System.
Embodiment 1
(1),
1, the nitrilotriacetic acid of 0.1mol is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols, is added
The 5ml concentrated sulfuric acids react 3h at 75 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 0 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl esters are dissolved in 100ml ammonium hydroxide, are vigorously stirred for 24 hours under 50 DEG C of water bath conditions.
Solvent is removed in vacuum distillation, obtains nitrilotriacetic acid triamide, is dried in vacuo.
4,0.05mol nitrilotriacetic acids triamide is dissolved in dimethyl sulfoxide, and under the conditions of 5 DEG C, 0.05mol hydroborations are added
Sodium is added dropwise 0.1mol boron trifluoride ether, or 0.1mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.Reaction finishes
Afterwards, water is slowly added dropwise to be quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, back flow reaction
Residual solid is dissolved in water by 1h, evaporation drying, is added the sodium hydroxide solution of 5mol/L, stirs 30min, evaporation drying,
Drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain ammonia triethylamine, yield 73%.
The technique of the nitrilotriacetic acid synthesis ammonia triethylamine is shown below：
(2),
1, the nitrilotriacetic acid of 0.2mol is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols, is added
The 10ml concentrated sulfuric acids react 5h at 90 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 5 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl esters are dissolved in 100ml ammonium hydroxide, are vigorously stirred for 24 hours under 50 DEG C of water bath conditions.
Solvent is removed in vacuum distillation, obtains nitrilotriacetic acid triamide, is dried in vacuo.
4,0.1mol nitrilotriacetic acids triamide is dissolved in dimethyl sulfoxide, and under the conditions of 10 DEG C, 0.2mol hydroborations are added
Sodium is added dropwise 0.3mol boron trifluoride ether, or 0.3mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.Reaction finishes
Afterwards, water is slowly added dropwise to be quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, back flow reaction
Residual solid is dissolved in water by 1h, evaporation drying, is added the sodium hydroxide solution of 5mol/L, stirs 30min, evaporation drying,
Drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain ammonia triethylamine, yield 74%.
(3),
1, the nitrilotriacetic acid of 0.1mol is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols, is added
The 10ml concentrated sulfuric acids react 5h at 80 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 0 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl esters are dissolved in 100ml ammonium hydroxide, are vigorously stirred for 24 hours under 50 DEG C of water bath conditions.
Solvent is removed in vacuum distillation, obtains nitrilotriacetic acid triamide, is dried in vacuo.
4,0.05mol nitrilotriacetic acids triamide is dissolved in dimethyl sulfoxide, and under the conditions of 5 DEG C, 0.1mol hydroborations are added
Sodium is added dropwise 0.15mol boron trifluoride ether, or 0.15mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.It has reacted
Bi Hou is slowly added dropwise water and is quenched, then evaporation drying, and the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, back flow reaction
Residual solid is dissolved in water by 1h, evaporation drying, is added the sodium hydroxide solution of 5mol/L, stirs 30min, evaporation drying,
Drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain ammonia triethylamine, yield 76%.
Embodiment 2：
(1),
1, it by the ethylenediamine tetra-acetic acid of 0.1mol, is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols,
The 5ml concentrated sulfuric acids are added, 3h is reacted at 75 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 0 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains ethylenediamine tetrem
Sour tetra-ethyl ester.
3,0.05mol ethylenediamine tetra-acetic acid tetra-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, 5 equivalent ammonia is added
Methanol is added 1% sodium methoxide, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains ethylenediamine tetrem
Sour four amides, vacuum drying.
4, four amide of 0.05mol ethylenediamine tetra-acetic acids is dissolved in dimethyl sulfoxide, and under the conditions of 5 DEG C, 0.05mol boron is added
Sodium hydride is added dropwise 0.1mol boron trifluoride ether, or 0.1mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.Reaction
After, water is slowly added dropwise and is quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, reflux is anti-
It answers 1h, evaporation drying to be dissolved in water residual solid, the sodium hydroxide solution of 5mol/L is added, stir 30min, evaporation is dry
It is dry, drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain Ethylenedinitrilotetraacetic Acid, yield 83%.
(2),
1, it by the ethylenediamine tetra-acetic acid of 0.2mol, is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols,
The 10ml concentrated sulfuric acids are added, 5h is reacted at 90 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 5 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains ethylenediamine tetrem
Sour tetra-ethyl ester.
3,0.1mol ethylenediamine tetra-acetic acid tetra-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, 10 equivalent ammonia is added
Methanol is added 10% sodium methoxide, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains ethylenediamine tetrem
Sour four amides, vacuum drying.
4, four amide of 0.1mol ethylenediamine tetra-acetic acids is dissolved in dimethyl sulfoxide, and under the conditions of 10 DEG C, 0.2mol boron is added
Sodium hydride is added dropwise 0.3mol boron trifluoride ether, or 0.3mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.Reaction
After, water is slowly added dropwise and is quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, reflux is anti-
It answers 1h, evaporation drying to be dissolved in water residual solid, the sodium hydroxide solution of 5mol/L is added, stir 30min, evaporation is dry
It is dry, drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain Ethylenedinitrilotetraacetic Acid, yield 85%.
(3),
1, it by the ethylenediamine tetra-acetic acid of 0.15mol, is added in the single-necked flask of 500ml, 250ml absolute ethyl alcohols is added
In, the 10ml concentrated sulfuric acids are added, 5h is reacted at 80 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 0 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains ethylenediamine tetrem
Sour tetra-ethyl ester.
3,0.1mol ethylenediamine tetra-acetic acid tetra-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, 8 equivalent ammonia is added
Methanol is added 5% sodium methoxide, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains ethylenediamine tetrem
Sour four amides, vacuum drying.
4, four amide of 0.1mol ethylenediamine tetra-acetic acids is dissolved in dimethyl sulfoxide, and under the conditions of 10 DEG C, 0.15mol boron is added
Sodium hydride is added dropwise 0.2mol boron trifluoride ether, or 0.2mol lithium aluminium hydride reductions is added, and is warming up to room temperature reaction overnight.Reaction
After, water is slowly added dropwise and is quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, after drop finishes, reflux is anti-
It answers 1h, evaporation drying to be dissolved in water residual solid, the sodium hydroxide solution of 5mol/L is added, stir 30min, evaporation is dry
It is dry, drying solid is dissolved in anhydrous ether, is filtered, is rotated ether, obtain Ethylenedinitrilotetraacetic Acid, yield 86%.
Embodiment 3
(1),
1, the diethylene triamine pentacetic acid (DTPA) of 0.1mol is added in the single-necked flask of 500ml, 250ml absolute ethyl alcohols is added
In, the 5ml concentrated sulfuric acids are added, 3h is reacted at 15 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 0 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.05mol diethylene triamine pentacetic acid (DTPA) penta-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, are added 5 and work as
Ammonia methanol is measured, 1% sodium methoxide is added, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains divinyl
Five amide of pentaacetic acid, vacuum drying.
4, five amide of 0.05mol diethylene triamine pentacetic acid (DTPA)s is dissolved in dimethyl sulfoxide, under the conditions of 5 DEG C, is added
0.05mol sodium borohydrides are added dropwise 0.1mol boron trifluoride ether, or 0.1mol lithium aluminium hydride reductions are added, and are warming up to room temperature reaction
Overnight.After completion of the reaction, water is slowly added dropwise to be quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, drop finishes
Afterwards, residual solid is dissolved in water by back flow reaction 1h, evaporation drying, and the sodium hydroxide solution of 5mol/L is added, stirring
Drying solid is dissolved in anhydrous ether by 30min, evaporation drying, and filtering rotates ether, obtains five second of diethylenetriamine
Amine, yield 84%.
(2),
1, the diethylene triamine pentacetic acid (DTPA) of 0.2mol is added in the single-necked flask of 500ml, 250ml absolute ethyl alcohols is added
In, the 10ml concentrated sulfuric acids are added, 5h is reacted at 90 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 5 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.1mol diethylene triamine pentacetic acid (DTPA) penta-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, are added 10 and work as
Ammonia methanol is measured, 10% sodium methoxide is added, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains divinyl
Five amide of pentaacetic acid, vacuum drying.
4, five amide of 0.1mol diethylene triamine pentacetic acid (DTPA)s is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, is added
0.2mol sodium borohydrides are added dropwise 0.3mol boron trifluoride ether, or 0.3mol lithium aluminium hydride reductions are added, and are warming up to and react at room temperature
Night.After completion of the reaction, water is slowly added dropwise to be quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, drop finishes
Afterwards, residual solid is dissolved in water by back flow reaction 1h, evaporation drying, and the sodium hydroxide solution of 5mol/L is added, stirring
Drying solid is dissolved in anhydrous ether by 30min, evaporation drying, and filtering rotates ether, obtains five second of diethylenetriamine
Amine, yield 87%.
(3),
1, the diethylene triamine pentacetic acid (DTPA) of 0.15mol is added in the single-necked flask of 500ml, the anhydrous second of 250ml is added
In alcohol, the 10ml concentrated sulfuric acids are added, 4h is reacted at 85 DEG C.
2, it after being cooled to room temperature, is concentrated under reduced pressure.100ml dichloromethane is added, 10% hydroxide is added dropwise under the conditions of 5 DEG C
Sodium solution detaches organic layer after pH test paper is in alkalinity, and anhydrous magnesium sulfate drying is filtered, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.1mol diethylene triamine pentacetic acid (DTPA) penta-ethyl esters are dissolved in 50ml organic solvent dimethyl sulfoxides, are added 10 and work as
Ammonia methanol is measured, 7% sodium methoxide is added, is vigorously stirred for 24 hours under 50 DEG C of water bath conditions.Solvent is removed in vacuum distillation, obtains divinyl
Five amide of pentaacetic acid, vacuum drying.
4, five amide of 0.1mol diethylene triamine pentacetic acid (DTPA)s is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, is added
0.1mol sodium borohydrides are added dropwise 0.2mol boron trifluoride ether, or 0.2mol lithium aluminium hydride reductions are added, and are warming up to and react at room temperature
Night.After completion of the reaction, water is slowly added dropwise to be quenched, then evaporation drying, the hydrochloric acid solution of 5mol/L is slowly added dropwise, drop finishes
Afterwards, residual solid is dissolved in water by back flow reaction 1h, evaporation drying, and the sodium hydroxide solution of 5mol/L is added, stirring
Drying solid is dissolved in anhydrous ether by 30min, evaporation drying, and filtering rotates ether, obtains five second of diethylenetriamine
Amine, yield 88%.
Embodiment 4
Inhibitor made of products configuration obtained by Examples 1 to 3 and conventional shale control agent (are selected into hexamethylene diamine
Class inhibitor and polyamine class inhibitor) contrast experiment is carried out, using linear expansion rate and rolling rate of recovery, to evaluate above-mentioned implementation
Inhibitor performance prepared by example, concrete operation step reference《SY-T5613-2000 mud shale physicochemical property test methods》With
《SY/T5971-1994 water fillings clay stabilizer method of evaluating performance》If unspecified, the percentage that is arrived involved in embodiment
Number " % " is that the data that measure after mass percent experiments are as shown in Table 1 and Table 2, and linear expansion rate is lower, illustrates inhibitor
Rejection it is better；Rolling rate of recovery is higher, illustrates that the rejection of inhibitor is better.
1 linear expansion rate of table
Influence of the 2 inhibitor dosage of table to linear expansion rate
3 rolling rate of recovery of table (it is 240 DEG C to roll temperature)
Influence of the 4 inhibitor dosage of table to the rate of recovery (it is 240 DEG C to roll temperature)
| Component | The rate of recovery/% |
| Ammonia triethylamine obtained by 1% embodiment 1 | 65.21 |
| Ammonia triethylamine obtained by 2% embodiment 1 | 70.42 |
| Ammonia triethylamine obtained by 3% embodiment 1 | 75.55 |
| Ethylenedinitrilotetraacetic Acid obtained by 1% embodiment 2 | 72.43 |
| Ethylenedinitrilotetraacetic Acid obtained by 2% embodiment 2 | 78.43 |
| Ethylenedinitrilotetraacetic Acid obtained by 3% embodiment 2 | 83.16 |
| Five ethamine of diethylenetriamine obtained by 1% embodiment 3 | 78.58 |
| Five ethamine of diethylenetriamine obtained by 2% embodiment 3 | 83.46 |
| Five ethamine of diethylenetriamine obtained by 3% embodiment 3 | 88.55 |
The linear expansion rate of table 1 the result shows that, under conditions of identical dosage, ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethyl
Five ethamine of alkene triamine shows excellent rejection, has better rejection than similar product hexamethylene diamine and polyamine.
Influence of the inhibitor dosage of table 2 to linear expansion rate shows the increase with inhibitor dosage, linear expansion rate
It reduces, rejection is more preferable, and increasing with primary amine group quantity, and rejection is more preferable.
The rolling rate of recovery of table 3 the result shows that, the rolling of ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, five ethamine of diethylenetriamine
The rate of recovery is all higher than the rolling rate of recovery of hexamethylene diamine and polyamine, illustrates triethylamine, Ethylenedinitrilotetraacetic Acid, five ethamine of diethylenetriamine
With preferable rejection, and increasing with primary amine group quantity, rejection is more preferable.Also indicate that institute of the present invention simultaneously
The inhibitor of offer shows excellent at high operating temperatures.
Influence of the inhibitor dosage of table 4 to rolling rate of recovery shows the increase with inhibitor dosage, rolling rate of recovery
Increase, rejection is more preferable, and increasing with primary amine group quantity, and rejection is more preferable, while also indicating that institute of the present invention
The inhibitor of offer shows excellent at high operating temperatures.
The raw material that Examples 1 to 3 is configured can individually be configured to inhibitor with clear water, also can mutually mix, then with clear water
It is configured to inhibitor.
The above is only a preferred embodiment of the present invention, it is noted that the invention is not limited in aforesaid way,
Without departing from the principles of the invention, moreover it is possible to be further improved, these improvement also should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of Ultra-low molecular weight intercalation inhibitor, which is characterized in that by ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethylenetriamine
Any one or a few in five ethamine is mixed into 0.5~3% weight ratio, remaining is water；
The structural formula of the ammonia triethylamine is：
The structural formula of the Ethylenedinitrilotetraacetic Acid is：
The structural formula of five ethamine of the diethylenetriamine is：
2. a kind of Ultra-low molecular weight intercalation inhibitor according to claim 1, which is characterized in that the ammonia triethylamine is by ammonia
Triacetic acid synthesizes, and the structural formula of nitrilotriacetic acid is：
The Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediamine tetra-acetic acid, and the structural formula of ethylenediamine tetra-acetic acid is：
Five ethamine of the diethylenetriamine is synthesized by diethylene triamine pentacetic acid (DTPA), and the structural formula of diethylene triamine pentacetic acid (DTPA) is：
3. the preparation method of the Ultra-low molecular weight intercalation inhibitor according to any one of claim 1~2, feature exist
In steps are as follows：
S1, the raw material of 0.1~0.2mol is added in the single-necked flask of 500ml, is added in 250ml absolute ethyl alcohols, addition 5~
The 10ml concentrated sulfuric acids react 3~5h at 75~90 DEG C, obtain product；
S2, it after the obtained products of step S1 are cooled to room temperature, is concentrated under reduced pressure, 100ml dichloromethane is added, in 0~5 DEG C of condition
The sodium hydroxide solution of lower dropwise addition 10% detaches organic layer, anhydrous magnesium sulfate drying after pH test paper is in alkalinity, and filtering is steamed
It evaporates, obtains the product with carboxylic acid, ethyl ester functional group；
The product with carboxylic acid, ethyl ester functional group obtained in S3, step S2, takes 0.05~0.1mol to be dissolved in 50ml organic solvents
In, the methanolic ammonia solution of 5~10 equivalents is added, adds 1~10% sodium methoxide, is vigorously stirred under 50 DEG C of water bath conditions for 24 hours,
Solvent is removed in vacuum distillation, obtains product；
S4, the 0.05~0.1mol products obtained in step S3 are dissolved in organic solvent, under the conditions of 5~10 DEG C, is added
0.1~0.3mol boron trifluoride ether is added dropwise in 0.05~0.2mol sodium borohydrides, is warming up to room temperature reaction 12h；Reaction finishes
Afterwards, water is slowly added dropwise to be quenched, then evaporation drying, dropwise addition 0.1~0.3mol boron trifluoride ether, or addition 0.1~
0.3mol lithium aluminium hydride reductions drip back flow reaction 1h, evaporation drying after finishing and are dissolved in water residual solid, the hydrogen of 5mol/L is added
Sodium hydroxide solution stirs 30min, and drying solid is dissolved in anhydrous ether, then filters by evaporation drying, and rotary evaporation falls
Ether obtains product；
S5, reaction kettle is added according to required ratio in step S4 resulting products, is stirred after clear water is added, is configured to ultra-low molecular
Measure intercalation inhibitor.
4. a kind of preparation method of Ultra-low molecular weight intercalation inhibitor according to claim 3, which is characterized in that step S1
Described in raw material be nitrilotriacetic acid, ethylenediamine tetra-acetic acid, one kind in diethylene triamine pentacetic acid (DTPA).
5. a kind of preparation method of Ultra-low molecular weight intercalation inhibitor according to claim 3, which is characterized in that step S3
Described in organic solvent be tetrahydrofuran, pyridine, n,N-Dimethylformamide, n,N-dimethylacetamide, in dimethyl sulfoxide
One kind.
6. a kind of preparation method of Ultra-low molecular weight intercalation inhibitor according to claim 3, which is characterized in that step S3
The step of methanolic ammonia solution of middle addition, can be replaced and be passed through ammonia or addition ammonium hydroxide.
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| CN108822811A (en) * | 2018-08-28 | 2018-11-16 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of gas well horizontal well slim-hole polyamines high inhibition caving-preventing drilling fluid and preparation method |
| CN109762535B (en) * | 2019-02-12 | 2021-01-29 | 西南石油大学 | Shale intercalation inhibitor prepared from hyperbranched polyamine |
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