CN106520085B - A kind of dendritic polyether shale inhibitor and preparation method and application - Google Patents
A kind of dendritic polyether shale inhibitor and preparation method and application Download PDFInfo
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- CN106520085B CN106520085B CN201610953281.1A CN201610953281A CN106520085B CN 106520085 B CN106520085 B CN 106520085B CN 201610953281 A CN201610953281 A CN 201610953281A CN 106520085 B CN106520085 B CN 106520085B
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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
- 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
- C09K8/035—Organic additives
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08G83/004—After treatment of dendrimers
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- 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
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Abstract
The invention discloses a kind of dendritic polyether shale inhibitors and preparation method and application.The inhibitor is by end amido dendritic and epoxyalkane dendritic polyether shale inhibitor obtained by the reaction.The dendritic polyether shale inhibitor that the present invention is prepared has excellent shale inhibition energy, shale hydration expansion and dispersion can be significantly inhibited, and there is good coordinate repression with sylvite, with performance is prominent, environmental acceptability is good, action effective is long.
Description
Technical field
The present invention relates to a kind of drilling fluid shale inhibitors, and in particular to a kind of dendritic polyether shale inhibitor
And preparation method and application, belong to petroleum works field.
Background technology
Wellbore stability is always the worldwide technological puzzle perplexed in oil/gas drilling engineering.Data are shown according to statistics, about
75% stratum for boring chance is mud shale stratum, and 90% borehole well instability problem is happened at mud shale stratum.Shale hydration is
One of the main reason for leading to borehole well instability.For a long time, people have carried out numerous studies, and carry for shale hydration mechanism
Corresponding technical cue is gone out, has developed various types of shale inhibitors in succession, such as inorganic salts, cationic polymer, changed
Property pitch, amphoteric ion polymer, methyl glucoside, silicate, positive colloid, polymeric alcohol, organic salt, organic amine etc..More than
It states inhibitor and constructs different anti-collapse water base drilling fluid systems for main inorganic agent, field application obtains certain success, but still
There are various limitations.As although potassium chloride inhibition is excellent, using excessive concentration, easily well logging is surveyed in interference, and environment is made
Into influence；There are environmental issues for asphalt product；Silicate has excellent closure rejection, but its rheological characteristic is easily by pH shadows
It rings；Glucose glycoside inorganic agent dosage is big.Therefore, it is still very necessary to develop new and effective shale inhibitor.
Dendritic in the 1980s mid-term occur, be a kind of three-dimensional, high-sequential, can be from molecular level
Upper control, the Novel polymer for designing bulk of molecule, shape, structure and function group.Dendritic is main
Have following structure feature：(1) accurate molecular structure, the geometrical symmetry of (2) height, (3) a large amount of functional group, (4) point
There are cavitys, (5) relative molecular mass in son to have controllability, and (6) molecule sheet is as nano-scale.Dendritic is above-mentioned
Design feature makes it have some special properties and function, so as to show potential application value in different field, at present
The concern of numerous researchers is obtained.In drilling fluid field, people also begin to attempt to inhibit mud page using dendritic
Rock hydration swelling and dispersion.
103917623 A of Chinese patent document CN disclose a kind of hyperbranched poly lysine in subsurface mineral oil and natural
In the exploitation in gas mineral deposit, exploitation and completion and the purposes in deep-well, especially in water-based drilling magma, completion fluid or volume increase
As the purposes of shale control agent in liquid.The inhibitor is had excellent performance, nontoxic, biodegradable, and will not be tired out in vivo
Product.
104130758 A of Chinese patent document CN disclose a kind of dendroid polyamines base for mud rock drilling well and polymerize
Object drilling fluid.By dendroid polyamines based polyalcohol, drilling fluid bentonite, soda ash, polymer coating agent, polyacrylic acid potassium, hydrolysis
Polyacrylonitrile ammonium salt, anti-mud drum lubricant and water composition.The inhibition of drilling fluid can be improved using polyamines base dendritic
Property, drilling fluid can also be increased substantially to clay and drilling cuttings inhibition, reduce clay rock plasticity, the water suction for avoiding clay rock is swollen
Swollen reduction frictional resistance prevents bit balling with disperseing, conducive to rate of penetration, guarantee downhole safety is improved.
104250380 A of Chinese patent document CN disclose a kind of dendritic and dendritic monomer and
Preparation method and application.The dendritic monomer can be used as comonomer to prepare oil field dissaving polymer, institute
It obtains dissaving polymer and may be used as drilling fluid inhibition fluid loss additive, flocculant, coating agent, the polymer displacement of reservoir oil of temperature-resistant anti-salt
Agent, fracturing fluid gelatinizer etc., the monomer can be used for preparing the branched water-soluble polymer season emulsion polymerization of other purposes
Internal surfactants.
104250358 A of Chinese patent document CN disclose a kind of hyper branched copolymer and its preparation method and application.It should
The apparent viscosity of 1 mass % aqueous solutions of hyper branched copolymer is 20-60mPa.s, in high temperature (180 DEG C) (saturated brine) with high salt and
There is preferable filtrate reducing characteristic under the conditions of high calcium (10% calcium chloride), it is right while guarantee drilling fluid good rejection ability
The filter loss of drilling fluid has no adverse effects.
104449596 A of Chinese patent document CN disclose a kind of polyether polyol shale control agent and its preparation and should
With.Using polyalcohol as initiator, catalyst, addition polymerization ethylene oxide (EO) and propylene oxide (PO) are made using KOH, with acid after reaction
It neutralizes, adsorbent absorption, is filtered with filter, shale-control agent for drilling fluid polyether polyol is made；The polyether polyol page
Rock inhibitor, which has, to be inhibited hydration and expansion of clay, stabilizing borehole, improves drilling fluid lubricating performance, prevents a variety of works such as bit balling
With and low toxicity, easily biological-degradable, meet green technology requirement.
Amanullah (SPE164162,2013) thinks according to the characteristics of dendritic：Dendritic
Three-dimensional manometer chondritic provides the foundation effectively to block the micro-nano hole of mud shale and crack；Dendritic surface has
Cation group is such as modified by a large amount of functional groups, can form multiple spot on mud shale surface and adsorb by force, can effectively inhibit shale hydration
And dispersion.In addition, by changing in the special micromolecular compound of dendritic internal cavities encapsulation or external surface functional group
Sex modification assigns the specific functions such as dendritic self assembly behavior and environment-responsive, will provide diversification for stabilizing borehole
Approach.Thus Amanullah predicts, dendritic inhibit mud shale surfaces externally and internally aquation, improve membrane efficiency of shale,
Resistance is delayed or even elimination pore pressure is transmitted, extends inhibition timeliness and While-drilling borehole reinforcing etc. dives with huge application
Power, and provide possibility for Future Development " intelligence " drilling fluid.
Although having carried out a large amount of research as shale-control agent for drilling fluid currently for polyether polyol, generally adopt
All it is linear polyether, dosage is often larger, and inhibition is still undesirable.Further, since it easily causes drilling fluid to blister
And increasing stick, have an adverse effect to drilling fluid rheology and filter loss.Therefore, for current polyethers shale control agent not
Foot uses for reference the characteristics of dendritic spherical structure, end group density are high, solution viscosity is low, develops environment-friendly type dendroid
Polyethers shale control agent, to solve the problems, such as strongly active Wellbore Stability.
Invention content
In view of the deficiencies of the prior art, the present invention provide a kind of dendritic polyether shale inhibitor and preparation method thereof with
Using.The dendritic polyether shale inhibitor has the advantages that dosage is few, and inhibition is excellent, environmental acceptability.
Technical scheme is as follows：
A kind of dendritic polyether shale inhibitor, the inhibitor are anti-by end amido dendritic and epoxyalkane
The modified product that should be obtained.
According to currently preferred, the end amido dendritic is polypropyleneimine dendritic (PPI)
Or polyamide-amide dendritic (PAMAM).
Preferably, the algebraically of the polypropyleneimine dendritic is 0 generation (G0) to 5 generations (G5)；Polyamide-amide tree
The algebraically of dendritic polymer is 0 generation (G0) to 5 generations (G5).
It is further preferred that the algebraically of the polypropyleneimine dendritic is 0 generation (G0) to 3 generations (G3)；Polyamides
The algebraically of amine-amine dendritic is 0 generation (G0) to 3 generations (G3).
According to currently preferred, core is caused as ethylenediamine, propane diamine, fourth in the center of the end amido dendritic
Diamines, pentanediamine, hexamethylene diamine or ammonia.
According to currently preferred, group of the epoxyalkane for one or both of ethylene oxide or propylene oxide
It closes.
According to currently preferred, the dendritic polyether shale inhibitor is faint yellow viscous liquid or faint yellow
Solid.
A kind of preparation method of dendritic polyether shale inhibitor is as follows including step：
Under vacuum, amido dendritic and epoxyalkane is held to react under the effect of the catalyst, waits to react
Pressure is down to constant in device, stops reaction；Through aging, cooling, discharging, acid neutralizes, desalination presses down to get dendritic polyether mud shale
Preparation.
According to currently preferred, the catalyst is one or both of sodium hydroxide, potassium hydroxide or sodium ethoxide
Above combination.
According to currently preferred, the mass ratio of the end amido dendritic and catalyst is：100:0.1~
100:1；Preferably, the mass ratio of end amido dendritic and catalyst is：100:0.1~100:0.5；The end amido
The molar concentration rate of dendritic and epoxyalkane is：1:(the end amido number of 4 × end amido dendritic)~
1:(the end amido number of 20 × end amido dendritic).
According to currently preferred, the reaction temperature is 90~150 DEG C；Preferably, the reaction temperature for 110~
130℃。
According to currently preferred, the acid is neutralized as glacial acetic acid or phosphoric acid is used to neutralize.
According to currently preferred, the ageing time is 1h.
It is as follows including step according to currently preferred, the preparation method of the dendritic polyether shale inhibitor：
End amido dendritic and catalyst are added in reactor, logical nitrogen purging vacuumizes；It is warming up to 60~
80 DEG C, epoxyalkane is added in, is reacted at a temperature of 90~150 DEG C, treat that reactor pressure is down to constant, stopping reaction；Through old
Change, cooling, discharging, acid neutralizes, desalination is up to dendritic polyether shale inhibitor.
Preferably, the addition rate of the epoxyalkane is 1~10g/min.
It is as follows including step according to currently preferred, the preparation method of the dendritic polyether shale inhibitor：
End amido dendritic and catalyst are added in reactor, logical nitrogen purging vacuumizes；It is warming up to 60~
80 DEG C, propylene oxide is added in, is reacted at a temperature of 90~150 DEG C；Treat that reactor pressure is down to constant, is cooled to 60~80
DEG C, ethylene oxide is added in, is reacted at a temperature of 90~130 DEG C, treats that reactor pressure is down to constant, stopping reaction；Through aging,
Cooling, discharging, acid neutralizes, desalination is up to dendritic polyether shale inhibitor.
Preferably, the molar concentration rate of the propylene oxide and ethylene oxide is 1:1~1:10.
Preferably, the addition rate of the propylene oxide is 1~8g/min, and the addition rate of ethylene oxide is 1~10g/
min。
A kind of application of dendritic polyether shale inhibitor, the dendritic polyether shale inhibitor coordinate with sylvite
Applied in drilling fluid.
According to currently preferred, the sylvite is potassium chloride, potassium bromide, potassium iodide, potassium sulfate, potassium carbonate, potassium nitrate,
The combination of one or more of potassium formate, potassium acetate or potassium citrate.
According to currently preferred, in the drilling fluid mass concentration of dendritic polyether shale inhibitor for 0.1~
5wt%, the mass concentration of sylvite is 0.5~15wt%；Preferably, dendritic polyether shale inhibitor matter in the drilling fluid
A concentration of 0.5~3wt% is measured, the mass concentration of sylvite is 3~10wt%.
According to the present invention, the end amido dendritic can market buy, can also be obtained by prior art preparation,
It can be found in：Chinese patent document 201110073112.6,201010586069.9 and 201210290336.7.
The dendritic polyether shale inhibitor of the present invention inhibits the main function mechanism of shale hydration expansion and dispersion
Have：
(1) end amido dendritic introduces a large amount of hydroxyl, surface is contained a large amount of by being reacted with epoxyalkane
Hydroxyl can be adsorbed on surface of clay, the hydrone of exclusion surface of clay absorption；(2) in the presence of having potassium ion, potassium ion pressure
Contracting clay diffusion electric double layer reduces the aquation repulsion of clay particle, while convenient for dendritic polyether shale inhibitor in clay
Surface forms stable monolayer adsorption, weakens the aquation of clay particle；(3) it is dramatically different with linear polymer, dendroid
The a large amount of functional group in polyethers surface makes its effect with surface of clay more strong；(4) similar to polymeric alcohol, dendritic polyether mud
There are coordinate repressions equally between potassium ion for shale control agent.Therefore, dendritic polyether of the present invention has prominent
The rejection gone out.
The present invention has the following advantages that compared with prior art：
(1) dendritic polyether shale inhibitor prepared by the present invention can effectively inhibit mud shale (particularly active mud page
Rock) hydration swelling and dispersion；
(2) dendritic polyether shale inhibitor prepared by the present invention is low using concentration；
(3) due to the dendritic polyether shale inhibitor outer surface of the invention prepared, there are a large amount of hydroxyls, can pass through
Multiple spot is adsorbed on mud shale surface, can effectively be inhibited shale hydration and dispersion, and be not easy desorption, therefore can be played long-acting work
With.
(4) the dendritic polyether shale inhibitor prepared by the present invention can act synergistically with potassium ion, show to protrude
Rejection.
Description of the drawings
Fig. 1 is the infrared spectrogram of dendritic polyether shale inhibitor prepared by embodiment 1.
Fig. 2 is the infrared spectrogram of dendritic polyether shale inhibitor prepared by embodiment 2.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but not limited to this.
Experimental method described in following embodiments simultaneously, is conventional method unless otherwise specified；The reagent and material
Material, unless otherwise specified, commercially obtains.
Using ethylenediamine as core is caused, methyl acrylate and ethylenediamine are reaction raw materials, pass through Michael addition reactions and acyl
Aminating reaction alternately, obtains the polyamide-amide dendritic (PAMAM-Gn, n are algebraically) of different algebraically, specific to close
Chinese patent document CN201110073112.6 is referred into step.
Using ethylenediamine as core is caused, acrylonitrile is repetitive unit, is alternately repeated and carries out N- alkylated reactions and polynitriles
Reduction reaction obtains the polypropyleneimine dendritic (PPI-Gn, n are algebraically) of different algebraically, synthetic method reference
Chinese patent document CN201010586069.9 and 201210290336.7.
Embodiment 1
0.1mol (51.6g) initiators G0PAMAM (ethylenediamine is core) polyamides is added in 250mL high-temperature high-pressure reaction kettles
Amine-amine dendritic and 0.2g potassium hydroxide lead to nitrogen sparge tube road and reaction kettle 3 times, then by reaction kettle after sealing
Inside vacuumize.Reaction kettle is heated, 1.2mol (52.8g) ethylene oxide is slowly added to by measuring tank when temperature rises to 80 DEG C,
All ethylene oxide is added in 10min.After ethylene oxide all adds in, it is warming up to 110 DEG C and temperature is maintained to stablize, when
When pressure drops to invariable in kettle, show that reaction terminates.Logical circulating water to room temperature, pressure release discharging, reaction product is used
Acetic acid neutralizes, and filters desalination, dendritic polyether shale inhibitor.
Synthetic route is as follows：
The infrared spectrogram of dendritic polyether shale inhibitor manufactured in the present embodiment is as shown in Figure 1.It can from Fig. 1
Go out, 3380cm-1For O-H stretching vibration absworption peaks, 2920cm-1For C-H stretching vibration absworption peaks, 1650cm-1It stretches and shakes for C=O
Dynamic absorption peak (amide I peaks), 1560cm-1For C-N-H bending vibrations absorption peak (amide II peaks), 1100cm-1It stretches and shakes for C-O
Dynamic absorption peak, shows that G0PAMAM is reacted with ethylene oxide, has obtained target product.
The dendritic polyether shale inhibitor of the polyamide-amide modification of different algebraically can be made using identical method,
It is denoted as PAMAM-G0-E, PAMAM-G1-E and PAMAM-G2-E respectively.
Embodiment 2
0.1mol (28.8g) initiators G0PPI (ethylenediamine is core) polypropylene is added in 250mL high-temperature high-pressure reaction kettles
Imines dendritic and 0.1g potassium hydroxide lead to nitrogen sparge tube road and reaction kettle 3 times after sealing, then will be in reaction kettle
It vacuumizes.Reaction kettle is heated, 0.8mol (46.4g) propylene oxide is slowly added to by measuring tank when temperature rises to 70 DEG C,
After all being added in 10min, it is warming up to 130 DEG C and temperature is maintained to stablize.When reacting kettle inner pressure no longer changes, lead to recirculated water
60 DEG C or so are cooled to, 0.8mol (35.2g) ethylene oxide is then added in by measuring tank, after all being added in 10min, heating
To 110 DEG C and temperature is maintained to stablize.With reaction carry out, reacting kettle inner pressure decline, when pressure drops to it is invariable when, table
Bright reaction terminates.Logical circulating water to room temperature, pressure release discharging, reaction product is neutralized with acetic acid, filters desalination, obtain dendroid
Polyethers shale inhibitor.
Synthetic route is as follows：
The infrared spectrogram of dendritic polyether shale inhibitor manufactured in the present embodiment is as shown in Figure 2.It can from Fig. 2
Go out, 3360cm-1For O-H stretching vibration absworption peaks, 2970cm-1For-CH3Stretching vibration absworption peak, 2930cm-1For-CH2It is flexible to shake
Dynamic absorption peak, 1570cm-1For C-N-H bending vibrations absorption peak (amide II peaks), 1470cm-1And 1380cm-1Respectively it is C-
CH3Asymmetric and symmetric curvature vibration absorption peak, 1100cm-1For C-O stretching vibration absworption peaks, show G0PPI and propylene oxide
It is reacted with ethylene oxide, has obtained target product.
The dendritic polyether of the polypropyleneimine modification of different algebraically can be made using identical method, be denoted as PPI- respectively
G0-PE, PPI-G1-PE and PPI-G2-PE.
Test example 1
Inhibition is evaluated
The dendritic polyether mud that dispersion experiment prepares embodiment 1,2 is rolled using the experiment of bentonite pulping and shale is inhibited
Shale control agent carries out experimental evaluation.
1. inhibit the experiment of bentonite pulping
The step of inhibiting the experiment of bentonite pulping be：Dendroid prepared by the 4g present invention is added in 400mL tap water to gather
Ether shale inhibitor adds in 10g drilling fluids after stirring and dissolving with sodium bentonite (Shandong Hua Wei bentonites Co., Ltd),
After stirring 20min under 10000rpm, slurries are transferred in aging tank, aging tank is taken out after 70 DEG C of heat rolling 16h, is cooled to room temperature.
Using the rheological characteristic of the fast rotational viscometer test slurries of ZNN-D6 six after 10000rpm stirrings 10min.Add 10g drilling fluids use
Sodium bentonite takes out aging tank after heat rolling 16h at 70 DEG C, is cooled to room temperature, test slurries after 10000rpm stirrings 10min
Rheological characteristic.Above-mentioned experimental procedure is repeated, until slurry viscosity exceeds instrument test range.
In order to investigate the synergistic effect of dendritic polyether shale inhibitor and sylvite, the mud shale suppression of test dendritic polyether
Inhibit the performance of bentonite pulping when preparation is used cooperatively with KCl, the wherein dosage of KCl is 12g.
Table 1 is different system readings with the variation of bentonite dosage
Table 2 is different system readings with the variation of bentonite dosage
Table 3 is different system readings with the variation of bentonite dosage
Table 4 is different system readings with the variation of bentonite dosage
From table 1 and 3 test result of table it is found that after adding in the dendritic polyether shale inhibitor that the present invention is prepared,
Compared with blank sample, with the increase of bentonite dosage, 600 turns of readings, 300 turns of readings and 3 turns of reading increases are relatively slow,
Show that the dendritic polyether energy relative efficiency being prepared inhibits hydration and expansion of clay and dispersion.It can from table 2 and 4 test result of table
Know, the dendritic polyether that is prepared of the present invention with after KCl compoundings, with the increase of bentonite dosage, 600 turns of readings, 300 turns
Reading and 3 turns of reading increases are very slow, and are substantially better than individually added with the system of KCl.Show the dendroid being prepared
Synergistic effect can be effectively played after polyethers and KCl compoundings, effectively inhibits shale hydration expansion and dispersion.
2. shale rolls dispersion experiment
It is as follows that shale rolls the step of dispersion experiment：The certain mass present invention is added in 350mL tap water to be prepared
Dendritic polyether shale inhibitor, solution is transferred to aging tank after stirring and dissolving, while it is 2~5mm's to add in 50g grain sizes
Landwaste (is derived from Shengli Oil Field dune shape).Landwaste with normal saline solution is cleaned after 77 DEG C of heat rolling 16h and crosses 40 mesh standard sieves, is tailed over
It weighs after drying 4h at 105 DEG C, the ratio of landwaste quality and initial mass after drying is the landwaste rate of recovery, with percentage table
Show.
In order to investigate the synergistic effect of dendritic polyether and sylvite, rock when test dendritic polyether is used cooperatively with KCl
Consider the rate of recovery to be worth doing, the wherein dosage of KCl is 10.5g
The landwaste rate of recovery of the different shale control agents of table 5
| Test sample | The landwaste rate of recovery (%) | Test sample | The landwaste rate of recovery (%) |
| Blank sample | 20.6 | 3%KCl | 43.4 |
| 1%PAMAM-G0-E | 41.6 | 1%PAMAM-G0-E+3%KCl | 56.0 |
| 1%PAMAM-G1-E | 43.0 | 1%PAMAM-G1-E+3%KCl | 58.2 |
| 1%PAMAM-G2-E | 46.4 | 1%PAMAM-G2-E+3%KCl | 65.3 |
Note：Landwaste used is system in Tahe Oilfield well 3170m landwaste.
The landwaste rate of recovery of the different shale control agents of table 6
Note：Landwaste used is system in Tahe Oilfield well 2900m landwaste.
From table 5,6 as can be seen that dendritic polyether shale inhibitor of the present invention can effectively inhibit mud shale
Hydration swelling and dispersion, compared with clear water, the landwaste rate of recovery significantly improves；It is further with the use of the rear landwaste rate of recovery with KCl
It improves, shows that the two has significant synergistic effect.
Claims (12)
1. a kind of dendritic polyether shale inhibitor, which is characterized in that the inhibitor be by end amido dendritic with
Epoxyalkane modified product obtained by the reaction；
The molar concentration rate of the end amido dendritic and epoxyalkane is 1:12 or 1:16；
The end amido dendritic polymerize for polypropyleneimine dendritic (PPI) or polyamide-amide dendroid
Object (PAMAM).
2. dendritic polyether shale inhibitor according to claim 1, which is characterized in that the polypropyleneimine branch
The algebraically of shaped polymer is 0 generation (G0) to 5 generations (G5)；The algebraically of polyamide-amide dendritic is 0 generation (G0) to 5 generations
(G5)。
3. dendritic polyether shale inhibitor according to claim 1, which is characterized in that the epoxyalkane is epoxy
The combination of one or both of ethane or propylene oxide.
4. dendritic polyether shale inhibitor according to claim 1, which is characterized in that the dendritic polyether mud page
Rock inhibitor is faint yellow viscous liquid or faint yellow solid.
It is 5. as follows including step such as the preparation method of claim 1-4 any one of them dendritic polyether shale inhibitors：
Under vacuum, amido dendritic and epoxyalkane is held to react under the effect of the catalyst, treated in reactor
Pressure is down to constant, stopping reaction；Through aging, cooling, discharging, acid neutralizes, desalination inhibits to get dendritic polyether mud shale
Agent；
The molar concentration rate of the end amido dendritic and epoxyalkane is 1:12 or 1:16；
The end amido dendritic polymerize for polypropyleneimine dendritic (PPI) or polyamide-amide dendroid
Object (PAMAM).
6. the preparation method of dendritic polyether shale inhibitor according to claim 5, which is characterized in that the catalysis
Combination of the agent for one or more of sodium hydroxide, potassium hydroxide or sodium ethoxide.
7. the preparation method of dendritic polyether shale inhibitor according to claim 5, which is characterized in that the end amine
The mass ratio of base dendritic and catalyst is：100:0.1~100:1.
8. the preparation method of dendritic polyether shale inhibitor according to claim 5, which is characterized in that the reaction
Temperature is 90~150 DEG C；The ageing time is 1h.
9. the preparation method of dendritic polyether shale inhibitor according to claim 5, which is characterized in that the branch
The preparation method of shape polyethers shale inhibitor is as follows including step：
End amido dendritic and catalyst are added in reactor, logical nitrogen purging vacuumizes；It is warming up to 60~80
DEG C, epoxyalkane is added in, is reacted at a temperature of 90~150 DEG C, treats that reactor pressure is down to constant, stopping reaction；Through aging,
Cooling, discharging, acid neutralizes, desalination is up to dendritic polyether shale inhibitor；
The addition rate of the epoxyalkane is 1~10g/min.
10. the preparation method of dendritic polyether shale inhibitor according to claim 5, which is characterized in that the tree
The preparation method of dendritic polyether shale inhibitor is as follows including step：
End amido dendritic and catalyst are added in reactor, logical nitrogen purging vacuumizes；It is warming up to 60~80
DEG C, propylene oxide is added in, is reacted at a temperature of 90~150 DEG C；Treat that reactor pressure is down to constant, is cooled to 60~80 DEG C,
Ethylene oxide is added in, is reacted at a temperature of 90~130 DEG C, treats that reactor pressure is down to constant, stopping reaction；Through aging, cold
But, discharging, acid neutralization, desalination are up to dendritic polyether shale inhibitor；
The molar concentration rate of the propylene oxide and ethylene oxide is 1:1~1:10；
The addition rate of the propylene oxide is 1~8g/min, and the addition rate of ethylene oxide is 1~10g/min.
11. such as the application of claim 1-4 any one of them dendritic polyether shale inhibitors, the dendritic polyether mud
Shale control agent is with sylvite fit applications in drilling fluid；The quality of dendritic polyether shale inhibitor is dense in the drilling fluid
It spends for 0.1~5wt%, the mass concentration of sylvite is 0.5~15wt%.
12. the application of dendritic polyether shale inhibitor according to claim 11, which is characterized in that the drilling fluid
Middle dendritic polyether shale inhibitor mass concentration is 0.5~3wt%, and the mass concentration of sylvite is 3~10wt%.
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| CN107794008A (en) * | 2017-10-25 | 2018-03-13 | 西南石油大学 | One kind synthesis hydridization polyamines drilling fluid inhibitor and preparation method thereof |
| CN107699213A (en) * | 2017-11-06 | 2018-02-16 | 中国石油集团川庆钻探工程有限公司 | Preparation method of polyamide inhibitor suitable for drilling fluid |
| CN107722261A (en) * | 2017-11-06 | 2018-02-23 | 中国石油集团川庆钻探工程有限公司 | Preparation method of polyamide inhibitor suitable for drilling fluid |
| CN107699215A (en) * | 2017-11-06 | 2018-02-16 | 中国石油集团川庆钻探工程有限公司 | Preparation method of polyamide inhibitor for drilling fluid |
| CN108192107B (en) * | 2017-12-29 | 2019-06-04 | 中国石油大学(华东) | A kind of shale stability agent and preparation method thereof |
| CN114014585B (en) * | 2021-11-10 | 2022-10-28 | 江苏盐砼新材料科技有限公司 | Anti-mud additive and preparation method thereof, compound early-strength polycarboxylate superplasticizer prepared by adopting anti-mud additive and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005119003A1 (en) * | 2004-06-04 | 2005-12-15 | Halliburton Energy Services, Inc. | Compositions and methods of stabilizing subterranean formations containing reactive shales |
| CN102633955A (en) * | 2012-04-19 | 2012-08-15 | 西南石油大学 | Anti-shearing polymer and preparation method thereof |
| CN103320112A (en) * | 2013-06-26 | 2013-09-25 | 西南石油大学 | Novel anti-shearing branch polymer oil displacement agent and synthetic method thereof |
| CN103917623A (en) * | 2011-07-28 | 2014-07-09 | 巴斯夫欧洲公司 | Use of hyperbranched polylysine as shale inhibitor |
| CN104130758A (en) * | 2013-05-03 | 2014-11-05 | 中国石油化工股份有限公司 | Dendritic multi-amino polymer drilling fluid used for mud rock well drilling |
| CN104250380A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two |
-
2016
- 2016-11-03 CN CN201610953281.1A patent/CN106520085B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005119003A1 (en) * | 2004-06-04 | 2005-12-15 | Halliburton Energy Services, Inc. | Compositions and methods of stabilizing subterranean formations containing reactive shales |
| CN103917623A (en) * | 2011-07-28 | 2014-07-09 | 巴斯夫欧洲公司 | Use of hyperbranched polylysine as shale inhibitor |
| CN102633955A (en) * | 2012-04-19 | 2012-08-15 | 西南石油大学 | Anti-shearing polymer and preparation method thereof |
| CN104130758A (en) * | 2013-05-03 | 2014-11-05 | 中国石油化工股份有限公司 | Dendritic multi-amino polymer drilling fluid used for mud rock well drilling |
| CN104250380A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two |
| CN103320112A (en) * | 2013-06-26 | 2013-09-25 | 西南石油大学 | Novel anti-shearing branch polymer oil displacement agent and synthetic method thereof |
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