CN106281263A - 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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- CN106281263A CN106281263A CN201610644344.5A CN201610644344A CN106281263A CN 106281263 A CN106281263 A CN 106281263A CN 201610644344 A CN201610644344 A CN 201610644344A CN 106281263 A CN106281263 A CN 106281263A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Abstract
The present invention relates to a kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof, including following composition: any one or a few in ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethylenetriamine five ethamine, formulated with clear water according to the ratio of 0.5～3%, described ammonia triethylamine is synthesized by nitrilotriacetic acid, described Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediaminetetraacetic acid, described diethylenetriamine five ethamine is synthesized by diethylene triamine pentacetic acid (DTPA), add raw materials in dehydrated alcohol, react after adding concentrated sulphuric acid, adding organic solvent and be passed through ammonia, stirring distillation prepares product.The method can significantly improve the rejection of drilling fluid system, and heatproof reaches more than 240 DEG C, fully meet the demand of ultra-deep well drilling, effectively reduce problem hole instability occurring due to shale hydration dispersion, and synthesis technique is simple and environmentally-friendly, productivity is higher, low production cost, is suitable for industrialized production.
Description
Technical field
The invention belongs to oilfield drilling technical field, be specifically related to a kind of being applicable to and bore shale gas horizontal well horizontal segment
Water-base drilling fluid inhibitor and preparation method thereof.
Background technology
At present at home with 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, add drilling time and drilling cost.The hole instability of 75% occurs mainly in mud
Shale formation, particularly water-sensitive strata.
China's shale gas resources exploration is 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 levels well, shale horizontal well horizontal segment is longer, be typically in the range of 500～
2500m, the time increase that drilling fluid contacts with stratum, Shale Hydration is more serious.Drilling fluid filtrate enters layer reason gap, shale
Interior clay mineral water-swellable, the bulbs of pressure make tension force increase, and cause shale formation (locally) tensile fracture, occur that the borehole wall collapses
Collapse, the down hole problem such as undergauge.60%～70% external shale gas horizontal well uses oil base drilling fluid system, domestic completes
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, be conducive to protecting the advantage of reservoir, but exist not environmentally, the shortcoming such as cost is the highest.Water-base drilling fluid
Just the shortcoming that can overcome oil base drilling fluid, but the water-base drilling fluid of present stage is steady to mud stone or the strong retraction shale formation borehole wall
Determine aspect and yet suffer from problem, it is desirable to have further investigate pointedly.
On present stage oil field main use inorganic salt as inhibitor, but the inorganic salt of high concentration not only has a strong impact on
The rheological characteristic of drilling fluid, and underground environment is caused serious pollution.Conventional shale control agent is containing two primary amine groups
Group or polyetheramine, kiber alkyl amine, as inhibitor, has a strong impact on rheological characteristic and the dehydration wave making machine of drilling fluid, and alkyl two
The toxicity of amine is relatively big, does not meets environmental requirement.The shale control agent of polyamine class, in order to increase its water solublity, often increases in carbochain
Add hydroxyl and ehter bond, but this also reduces its rejection, and temperature resistance is limited in one's ability.
Along with the development of ultradeep well exploration and development, the research and development to shale control agent are had higher requirement.Owing to using
Water base drilling fluid system bores shale gas horizontal well, and water contacts with stratum at first, causes the clay hydration swelling on stratum, in order to suppress
The hydration swelling of clay, shale control agent must be rapidly inserted into clay interlayer, the hydrone of extrusion clay interlayer, reduce interlayer
Away from.Research finds, along with increasing of primary amine group quantity, inhibitor adsorption rate on clay is accelerated.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide pressing down of a kind of low-molecular-weight with 3～5 primary amine groups
Preparation and preparation method thereof, it not only can significantly improve the rejection of drilling fluid system, and heatproof reaches more than 240 DEG C, complete
The demand of full up sufficient ultra-deep well drilling, effectively reduces problem hole instability occurring due to shale hydration dispersion.And synthesis
Technique is simple and environmentally-friendly, and productivity is higher, low production cost, is suitable for industrialized production.
Technical scheme is as follows:
A kind of Ultra-low molecular weight intercalation inhibitor, by ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethylenetriamine five ethamine
Any one or a few is mixed into 0.5～3% weight ratio, and remaining is water；
The structural formula of described ammonia triethylamine is:
The structural formula of described Ethylenedinitrilotetraacetic Acid is:
The structural formula of described diethylenetriamine five ethamine is:
Further, described ammonia triethylamine is synthesized by nitrilotriacetic acid, and the structural formula of nitrilotriacetic acid is:
Described Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediaminetetraacetic acid, and the structural formula of ethylenediaminetetraacetic acid is:
Described diethylenetriamine five ethamine is synthesized by diethylene triamine pentacetic acid (DTPA), the structural formula of diethylene triamine pentacetic acid (DTPA)
For:
The present invention also provides for the preparation method of a kind of Ultra-low molecular weight intercalation inhibitor, and step is as follows:
S1, the raw material of 0.1～0.2mol is joined in the single port flask of 500ml, add in 250ml dehydrated alcohol, add
Enter 5～10ml concentrated sulphuric acids, react 3～5h at 75～90 DEG C, obtain product；
After S2, product step S1 obtained are cooled to room temperature, concentrating under reduced pressure, add 100ml dichloromethane, at 0～5 DEG C
Under the conditions of drip 10% sodium hydroxide solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, mistake
Filter, distillation, obtain the product of band carboxylic acid, ethyl ester functional group；
The product of the band carboxylic acid, ethyl ester functional group obtained in S3, step S2, taking 0.05～0.1mol, to be dissolved in 50ml organic
In solvent, (equivalent calculates the methanolic ammonia solution of addition 5～10 equivalents according to number of ester groups amount, as nitrilotriacetic acid has three carboxylic acid groups
, there are three ester groups in group after being esterified, then ester group adds the ammonia methanol of 5～10 times, and relative nitrilotriacetic acid needs to add 15
～the ammonia methanol of 30 times), adding 1～10% Feldalat NM, under 50 DEG C of water bath condition, be stirred vigorously 24h, decompression distillation is removed
Solvent, obtains product；
S4, by step S3 obtains 0.05～0.1mol product dissolve in organic solvent, under the conditions of 5～10 DEG C,
Add 0.05～0.2mol sodium borohydride, drip 0.1～0.3mol boron trifluoride diethyl etherate, or add 0.1～0.3mol hydrogenation
Aluminum lithium, is warming up to room temperature reaction 12h；After completion of the reaction, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise
The hydrochloric acid solution of 5mol/L, drips back flow reaction 1h after finishing, evaporation drying, residual solid is dissolved in water, and adds 5mol/L's
Sodium hydroxide solution, stirs 30min, evaporation drying, is dissolved in absolute ether by drying solid, then filters, rotary evaporation
Fall ether, obtain product；
S5, the product of step S4 gained is added reactor according to required ratio, add and stir after clear water, be configured to ultralow
Molecular weight intercalation inhibitor.
Raw material described in step S1 is the one in nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylene triamine pentacetic acid (DTPA)；
Organic solvent described in step S3 is oxolane, pyridine, DMF, N, N-dimethylacetamide
Amine, the one in dimethyl sulfoxide；
The step of the methanolic ammonia solution added in step S3, can be replaced and be passed through ammonia or add ammonia.
It is an advantage of the current invention that:
1, the product of the present invention, can be rapidly inserted into inside clay crystal layer, and its branched structure can firmly adsorb at clay crystal layer
Surface, the absorption water of extrusion interlayer, suppress surface hydration, effectively reduce owing to shale hydration dispersion occurs hole instability
Problem, be suitable to various soft mudstone stratum, saline bed, strong retraction stratum and other bad ground, ultra-long horizontal well can be met
The use of section environment；
2, not containing hydroxyl and ehter bond in inhibitor molecules, improve the heat-resisting property of inhibitor, temperature resistance can reach 240
DEG C, fully meeting the demand of ultra-deep well drilling, increasing of primary amine group quantity also reduces its bio-toxicity；
3, product needed raw material is cheap, and synthesis technique is simple and environmentally-friendly, and productivity is higher, is suitable for industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended that any limit to the present invention
System.
Embodiment 1
(1),
1, the nitrilotriacetic acid of 0.1mol is joined in the single port flask of 500ml, add in 250ml dehydrated alcohol, add
5ml concentrated sulphuric acid, reacts 3h at 75 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 0 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl ester is dissolved in 100ml ammonia, under 50 DEG C of water bath condition, is stirred vigorously 24h.
Solvent is removed in decompression distillation, obtains nitrilotriacetic acid Disnalon (Ferrer)., vacuum drying.
4,0.05mol nitrilotriacetic acid Disnalon (Ferrer). is dissolved in dimethyl sulfoxide, under the conditions of 5 DEG C, adds 0.05mol hydroboration
Sodium, drips 0.1mol boron trifluoride diethyl etherate, or adds 0.1mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.React complete
After, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip after finishing, back flow reaction
1h, evaporation drying, residual solid is dissolved in water, the sodium hydroxide solution of addition 5mol/L, stirring 30min, evaporation drying,
Being dissolved in absolute ether by drying solid, filter, rotation evaporates ether, obtains ammonia triethylamine, productivity 73%.
The technique of described nitrilotriacetic acid synthesis ammonia triethylamine is shown below:
(2),
1, the nitrilotriacetic acid of 0.2mol is joined in the single port flask of 500ml, add in 250ml dehydrated alcohol, add
10ml concentrated sulphuric acid, reacts 5h at 90 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 5 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl ester is dissolved in 100ml ammonia, under 50 DEG C of water bath condition, is stirred vigorously 24h.
Solvent is removed in decompression distillation, obtains nitrilotriacetic acid Disnalon (Ferrer)., vacuum drying.
4,0.1mol nitrilotriacetic acid Disnalon (Ferrer). is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, adds 0.2mol hydroboration
Sodium, drips 0.3mol boron trifluoride diethyl etherate, or adds 0.3mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.React complete
After, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip after finishing, back flow reaction
1h, evaporation drying, residual solid is dissolved in water, the sodium hydroxide solution of addition 5mol/L, stirring 30min, evaporation drying,
Being dissolved in absolute ether by drying solid, filter, rotation evaporates ether, obtains ammonia triethylamine, productivity 74%.
(3),
1, the nitrilotriacetic acid of 0.1mol is joined in the single port flask of 500ml, add in 250ml dehydrated alcohol, add
10ml concentrated sulphuric acid, reacts 5h at 80 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 0 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains nitrilotriacetic acid second
Ester.
3,0.05mol nitrilotriacetic acid ethyl ester is dissolved in 100ml ammonia, under 50 DEG C of water bath condition, is stirred vigorously 24h.
Solvent is removed in decompression distillation, obtains nitrilotriacetic acid Disnalon (Ferrer)., vacuum drying.
4,0.05mol nitrilotriacetic acid Disnalon (Ferrer). is dissolved in dimethyl sulfoxide, under the conditions of 5 DEG C, adds 0.1mol hydroboration
Sodium, drips 0.15mol boron trifluoride diethyl etherate, or adds 0.15mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.React
Bi Hou, is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drips after finishing, back flow reaction
1h, evaporation drying, residual solid is dissolved in water, the sodium hydroxide solution of addition 5mol/L, stirring 30min, evaporation drying,
Being dissolved in absolute ether by drying solid, filter, rotation evaporates ether, obtains ammonia triethylamine, productivity 76%.
Embodiment 2:
(1),
1, by the ethylenediaminetetraacetic acid of 0.1mol, join in the single port flask of 500ml, add in 250ml dehydrated alcohol,
Add 5ml concentrated sulphuric acid, react 3h at 75 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 0 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains ethylenediamine tetrem
Acid tetra-ethyl ester.
3,0.05mol ethylenediaminetetraacetic acid tetra-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 5 equivalent ammonia
Methanol, adds 1% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains ethylenediamine tetrem
Acid four amide, vacuum drying.
4,0.05mol ethylenediaminetetraacetic acid four amide is dissolved in dimethyl sulfoxide, under the conditions of 5 DEG C, adds 0.05mol boron
Sodium hydride, drips 0.1mol boron trifluoride diethyl etherate, or adds 0.1mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.Reaction
After, it being slowly added dropwise water and carry out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip after finishing, backflow is anti-
Answering 1h, evaporation drying, residual solid be dissolved in water, add the sodium hydroxide solution of 5mol/L, stir 30min, evaporation is dry
Dry, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains Ethylenedinitrilotetraacetic Acid, productivity 83%.
(2),
1, by the ethylenediaminetetraacetic acid of 0.2mol, join in the single port flask of 500ml, add in 250ml dehydrated alcohol,
Add 10ml concentrated sulphuric acid, react 5h at 90 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 5 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains ethylenediamine tetrem
Acid tetra-ethyl ester.
3,0.1mol ethylenediaminetetraacetic acid tetra-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 10 equivalent ammonia
Methanol, adds 10% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains ethylenediamine tetrem
Acid four amide, vacuum drying.
4,0.1mol ethylenediaminetetraacetic acid four amide is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, adds 0.2mol boron
Sodium hydride, drips 0.3mol boron trifluoride diethyl etherate, or adds 0.3mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.Reaction
After, it being slowly added dropwise water and carry out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip after finishing, backflow is anti-
Answering 1h, evaporation drying, residual solid be dissolved in water, add the sodium hydroxide solution of 5mol/L, stir 30min, evaporation is dry
Dry, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains Ethylenedinitrilotetraacetic Acid, productivity 85%.
(3),
1, by the ethylenediaminetetraacetic acid of 0.15mol, join in the single port flask of 500ml, add 250ml dehydrated alcohol
In, add 10ml concentrated sulphuric acid, react 5h at 80 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 0 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains ethylenediamine tetrem
Acid tetra-ethyl ester.
3,0.1mol ethylenediaminetetraacetic acid tetra-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 8 equivalent ammonia
Methanol, adds 5% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains ethylenediamine tetrem
Acid four amide, vacuum drying.
4,0.1mol ethylenediaminetetraacetic acid four amide is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, adds 0.15mol boron
Sodium hydride, drips 0.2mol boron trifluoride diethyl etherate, or adds 0.2mol lithium aluminium hydride reduction, be warming up to room temperature reaction overnight.Reaction
After, it being slowly added dropwise water and carry out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip after finishing, backflow is anti-
Answering 1h, evaporation drying, residual solid be dissolved in water, add the sodium hydroxide solution of 5mol/L, stir 30min, evaporation is dry
Dry, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains Ethylenedinitrilotetraacetic Acid, productivity 86%.
Embodiment 3
(1),
1, the diethylene triamine pentacetic acid (DTPA) of 0.1mol is joined in the single port flask of 500ml, add 250ml dehydrated alcohol
In, add 5ml concentrated sulphuric acid, react 3h at 15 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 0 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.05mol diethylene triamine pentacetic acid (DTPA) penta-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 5 and work as
Amount ammonia methanol, adds 1% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains divinyl
Pentaacetic acid five amide, vacuum drying.
4,0.05mol diethylene triamine pentacetic acid (DTPA) five amide is dissolved in dimethyl sulfoxide, under the conditions of 5 DEG C, adds
0.05mol sodium borohydride, drips 0.1mol boron trifluoride diethyl etherate, or adds 0.1mol lithium aluminium hydride reduction, be warming up to room temperature reaction
Overnight.After completion of the reaction, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip and finish
After, back flow reaction 1h, evaporation drying, residual solid is dissolved in water, adds the sodium hydroxide solution of 5mol/L, stirring
30min, evaporation drying, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains diethylenetriamine five second
Amine, productivity 84%.
(2),
1, the diethylene triamine pentacetic acid (DTPA) of 0.2mol is joined in the single port flask of 500ml, add 250ml dehydrated alcohol
In, add 10ml concentrated sulphuric acid, react 5h at 90 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 5 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.1mol diethylene triamine pentacetic acid (DTPA) penta-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 10 and work as
Amount ammonia methanol, adds 10% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains divinyl
Pentaacetic acid five amide, vacuum drying.
4,0.1mol diethylene triamine pentacetic acid (DTPA) five amide is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, adds
0.2mol sodium borohydride, drips 0.3mol boron trifluoride diethyl etherate, or adds 0.3mol lithium aluminium hydride reduction, be warming up to room temperature reaction mistake
Night.After completion of the reaction, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip and finish
After, back flow reaction 1h, evaporation drying, residual solid is dissolved in water, adds the sodium hydroxide solution of 5mol/L, stirring
30min, evaporation drying, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains diethylenetriamine five second
Amine, productivity 87%.
(3),
1, the diethylene triamine pentacetic acid (DTPA) of 0.15mol is joined in the single port flask of 500ml, add the anhydrous second of 250ml
In alcohol, add 10ml concentrated sulphuric acid, react 4h at 85 DEG C.
2, after being cooled to room temperature, concentrating under reduced pressure.Add 100ml dichloromethane, under the conditions of 5 DEG C, drip the hydroxide of 10%
Sodium solution, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and distillation obtains diethylenetriamine
Pentaacetic acid penta-ethyl ester.
3,0.1mol diethylene triamine pentacetic acid (DTPA) penta-ethyl ester is dissolved in 50ml organic solvent dimethyl sulfoxide, adds 10 and work as
Amount ammonia methanol, adds 7% Feldalat NM, is stirred vigorously 24h under 50 DEG C of water bath condition.Solvent is removed in decompression distillation, obtains divinyl
Pentaacetic acid five amide, vacuum drying.
4,0.1mol diethylene triamine pentacetic acid (DTPA) five amide is dissolved in dimethyl sulfoxide, under the conditions of 10 DEG C, adds
0.1mol sodium borohydride, drips 0.2mol boron trifluoride diethyl etherate, or adds 0.2mol lithium aluminium hydride reduction, be warming up to room temperature reaction mistake
Night.After completion of the reaction, it is slowly added dropwise water and carries out cancellation, then evaporation drying, be slowly added dropwise the hydrochloric acid solution of 5mol/L, drip and finish
After, back flow reaction 1h, evaporation drying, residual solid is dissolved in water, adds the sodium hydroxide solution of 5mol/L, stirring
30min, evaporation drying, drying solid is dissolved in absolute ether, filters, rotation evaporates ether, obtains diethylenetriamine five second
Amine, productivity 88%.
Embodiment 4
The inhibitor of the products configuration obtained by embodiment 1～3 (is selected hexamethylene diamine with conventional shale control agent
Class inhibitor and polyamine class inhibitor) carry out contrast experiment, use linear expansion rate and roll the response rate, evaluating above-mentioned enforcement
Inhibitor performance prepared by example, its concrete operation step with reference to " SY-T5613-2000 mud shale physicochemical property test method " and
" SY/T5971-1994 water filling clay stabilizer method of evaluating performance ", if unspecified, the percentage that relates in embodiment
Number " % " is mass percent. and as shown in Table 1 and Table 2, linear expansion rate is the lowest for the data recorded after test, and inhibitor is described
Rejection the best；Roll the response rate the highest, illustrate that the rejection of inhibitor is the best.
Table 1 linear expansion rate
The impact on linear expansion rate of the table inhibitor 2 dosage
Table 3 rolls the response rate (rolling temperature is 240 DEG C)
The impact (rolling temperature is 240 DEG C) on the response rate of the table 4 inhibitor dosage
| Component | The response rate/% |
| 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 |
| Diethylenetriamine five ethamine obtained by 1% embodiment 3 | 78.58 |
| Diethylenetriamine five ethamine obtained by 2% embodiment 3 | 83.46 |
| Diethylenetriamine five ethamine obtained by 3% embodiment 3 | 88.55 |
The linear expansion rate result of table 1 shows, under conditions of identical dosage, and ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethyl
Alkene triamine five ethamine all shows the rejection of excellence, has more preferable rejection than like product hexamethylene diamine and polyamine.
The impact of linear expansion rate is shown by the inhibitor dosage of table 2, along with the increase of inhibitor dosage, linear expansion rate
Reducing, rejection is more preferable, and increasing along with primary amine group quantity, rejection is more preferable.
The rolling response rate result of table 3 shows, ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, the rolling of diethylenetriamine five ethamine
The response rate is higher than the rolling response rate of hexamethylene diamine and polyamine, and triethylamine, Ethylenedinitrilotetraacetic Acid, diethylenetriamine five ethamine are described
There is preferable rejection, and increasing along with primary amine group quantity, rejection is more preferable.Also indicate that institute of the present invention simultaneously
The inhibitor provided shows excellence at high operating temperatures.
The impact rolling the response rate is shown by the inhibitor dosage of table 4, along with the increase of inhibitor dosage, rolls the response rate
Increasing, rejection is more preferable, and increasing along with primary amine group quantity, rejection is more preferable, also indicates that institute of the present invention simultaneously
The inhibitor provided shows excellence at high operating temperatures.
The raw material that embodiment 1～3 is configured, can individually and clear water is configured to inhibitor, it is possible to mix mutually, then with clear water
It is configured to inhibitor.
The above is only the 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 improve further, these improvement also should be regarded as protection scope of the present invention.
Claims (6)
1. a Ultra-low molecular weight intercalation inhibitor, it is characterised in that by ammonia triethylamine, Ethylenedinitrilotetraacetic Acid, diethylenetriamine
Any one or a few in five ethamine is mixed into 0.5～3% weight ratio, and remaining is water；
The structural formula of described ammonia triethylamine is:
The structural formula of described Ethylenedinitrilotetraacetic Acid is:
The structural formula of described diethylenetriamine five ethamine is:
A kind of Ultra-low molecular weight intercalation inhibitor the most according to claim 1, it is characterised in that described ammonia triethylamine is by ammonia
Triacetic acid synthesizes, and the structural formula of nitrilotriacetic acid is:
Described Ethylenedinitrilotetraacetic Acid is synthesized by ethylenediaminetetraacetic acid, and the structural formula of ethylenediaminetetraacetic acid is:
Described diethylenetriamine five ethamine is synthesized by diethylene triamine pentacetic acid (DTPA), and the structural formula of diethylene triamine pentacetic acid (DTPA) is:
3. according to a kind of Ultra-low molecular weight intercalation inhibitor described in any one in claim 1～2, it is characterised in that this
Invention also provides for the preparation method of a kind of Ultra-low molecular weight intercalation inhibitor, and step is as follows:
S1, the raw material of 0.1～0.2mol is joined in the single port flask of 500ml, adds in 250ml dehydrated alcohol, add 5～
10ml concentrated sulphuric acid, reacts 3～5h at 75～90 DEG C, obtains product；
After S2, product step S1 obtained are cooled to room temperature, concentrating under reduced pressure, add 100ml dichloromethane, 0～5 DEG C of condition
The sodium hydroxide solution of lower dropping 10%, until after pH reagent paper is alkalescence, separating organic layer, anhydrous magnesium sulfate is dried, and filters, and steams
Evaporate, obtain the product of band carboxylic acid, ethyl ester functional group；
The product of the band carboxylic acid, ethyl ester functional group obtained in S3, step S2, takes 0.05～0.1mol and is dissolved in 50ml organic solvent
In, add the methanolic ammonia solution of 5～10 equivalents, add 1～10% Feldalat NM, under 50 DEG C of water bath condition, be stirred vigorously 24h,
Solvent is removed in decompression distillation, obtains product；
S4, by step S3 obtains 0.05～0.1mol product dissolve in organic solvent, under the conditions of 5～10 DEG C, add
0.05～0.2mol sodium borohydride, drips 0.1～0.3mol boron trifluoride diethyl etherate, is warming up to room temperature reaction 12h；React complete
After, be slowly added dropwise water and carry out cancellation, then evaporation drying, dropping 0.1～0.3mol boron trifluoride diethyl etherate, or add 0.1～
0.3mol lithium aluminium hydride reduction, drips back flow reaction 1h after finishing, evaporation drying, residual solid is dissolved in water, and adds the hydrogen of 5mol/L
Sodium hydroxide solution, stirs 30min, evaporation drying, is dissolved in absolute ether by drying solid, then filters, and rotary evaporation falls
Ether, obtains product；
S5, the product of step S4 gained is added reactor according to required ratio, add and stir after clear water, be configured to ultra-low molecular
Amount intercalation inhibitor.
The preparation method of a kind of Ultra-low molecular weight intercalation inhibitor the most according to claim 3, it is characterised in that step S1
Described in raw material be the one in nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylene triamine pentacetic acid (DTPA).
The preparation method of a kind of Ultra-low molecular weight intercalation inhibitor the most according to claim 3, it is characterised in that step S3
Described in organic solvent be oxolane, pyridine, DMF, N,N-dimethylacetamide, in dimethyl sulfoxide
One.
The preparation method of a kind of Ultra-low molecular weight intercalation inhibitor the most according to claim 3, it is characterised in that step S3
The step of the methanolic ammonia solution of middle addition, can be replaced and be passed through ammonia or add ammonia.
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| 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 |
| 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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