CN109824597A - It is suitable for modification polyhistidyl of supermolecule shale control agent and preparation method thereof and the application in water-base drilling fluid - Google Patents
It is suitable for modification polyhistidyl of supermolecule shale control agent and preparation method thereof and the application in water-base drilling fluid Download PDFInfo
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Abstract
The present invention relates to water-base drilling fluid fields, and in particular to is suitable for modification polyhistidyl of supermolecule shale control agent and preparation method thereof and the application in water-base drilling fluid.Containing the structural unit for being connected with modified group shown in formula (1) on the histidine polymer main chain of the modification polyhistidyl, the histidine degree of polymerization of the histidine polymer main chain is 6-9.The modification polyhistidyl provided by the invention is a kind of degradable biological material, is had the advantages that environmental-friendly；When being used as shale control agent, by its supermolecule property, the hydration swelling of most important expansion mineral montmorillonite in shale can be effectively inhibited, there is shown excellent inhibitory effect and its temperature resistance is high.
Description
Technical field
The present invention relates to water-base drilling fluid fields, and in particular to is suitable for the modification polyhistidyl of supermolecule shale control agent
And preparation method thereof and the application in water-base drilling fluid.
Background technique
The exploration and development of shale gas promotes the upgrading adjustment readjusted the energy structure in China, accelerates China and marches toward from " oil "
The paces of " gas " have pushed the energy to develop to more clean direction.In the drilling process of shale gas, due to the water-sensitive of shale
Property, the probing of shale gas mostly uses oil base drilling fluid.Although oil base drilling fluid is inhibiting Shale Hydration expansion, prevent the borehole wall from losing
Steady aspect has very excellent performance.But the problems such as there are at high cost, pollutions for oil base drilling fluid greatly, processing is difficult, with environmental protection
Idea deepens continuously, develop have good shale inhibition can water-base drilling fluid replace the oil base drilling fluid gesture must
Row.And one of the water-base drilling fluid key technology for being used for shale gas probing is exactly shale control agent.
Potassium chloride (KCl) as shale control agent since its cost is not high, be obviously once used widely by inhibitory effect, but
Because of its higher dosage, if can be impacted to ecological environment without processing.In order to reduce the influence to environment, amine cation
And its derivative is used as shale control agent, but the performance of amine inhibitor is influenced by pH, this is unfavorable for answering at the scene
With.Then, polyetheramine and forms high-property water-based on its basis using its preferable rejection by as shale control agent
Drilling fluid, but the thermal stability of polyetheramine is bad, can hydrolyze failure at high temperature.There are also some acrylamide copolymers also by
As shale control agent, but there is also not environmentally or the problems such as inhibition is bad.
Summary of the invention
The purpose of the present invention is to provide a kind of modification polyhistidyl for being suitable for supermolecule shale control agent and its preparations
Method and the application in water-base drilling fluid, the modification polyhistidyl have environmental-friendly, inhibitory effect as shale control agent
Good and stable advantage.
To achieve the goals above, one aspect of the present invention provides a kind of modification poly group for being suitable for supermolecule shale control agent
Propylhomoserin, which is characterized in that contain shown in formula (1) on the histidine polymer main chain of the modification polyhistidyl and be connected with modified base
The structural unit of group；
The histidine degree of polymerization of the histidine polymer main chain is 6-9；
Formula (1)
Each R1It is each independently selected from the alkyl of C1-C6；X is selected from halogen；R2The alkylene of the C3-C10 replaced selected from hydroxyl
Base.
Second aspect of the present invention provides the preparation method of above-mentioned modified polyhistidyl, this method comprises:
(1) under alkaline condition, histidine or its salt are subjected to dehydration condensation, obtain polyhistidyl；
(2) in aqueous solvent, formula (1 ') compound represented and polyhistidyl are subjected to haptoreaction；
Formula (1 ')
Y is halogen, preferably Cl, Br or I.
The above-mentioned modified polyhistidyl of third aspect present invention offer is as supermolecule shale control agent in water-base drilling fluid
Application.
Fourth aspect present invention, which provides, a kind of contains above-mentioned modified polyhistidyl as the water base of supermolecule shale control agent
Drilling fluid.
Fifth aspect present invention puts on the application for stating water-base drilling fluid in oil/gas drilling.
The modification polyhistidyl provided by the invention is a kind of degradable biological material, is had the advantages that environmental-friendly；
When being used as shale control agent, by its supermolecule property, it is de- that most important expansion mineral illiteracy in shale can be effectively inhibited
The hydration swelling of stone, there is shown excellent inhibitory effect and its temperature resistance is high, it will help pushes water-base drilling fluid in shale gas
Development in probing provides a strong guarantee for more preferable exploitation shale gas.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of modification polyhistidyl for being suitable for supermolecule shale control agent, the modification poly group ammonia
Contain the structural unit that modified group is connected with shown in formula (1) on the histidine polymer main chain of acid；
The histidine degree of polymerization of the histidine polymer main chain is 6-9；
Formula (1)
Each R1It is each independently selected from the alkyl of C1-C6；X is selected from halogen；R2The alkylene of the C3-C10 replaced selected from hydroxyl
Base.
According to the present invention, the above method of the invention, should by a kind of obtained modification polyhistidyl for having oversubscription sub-feature
Modified polyhistidyl can pass through the electrostatic force of itself, hydrogen bond and hydrophobic work in the shale control agent as water-base drilling fluid
With equal intermolecular forces, high inhibition effect is played to act on rammell；Also, the modification poly group ammonia for having oversubscription sub-feature
Acid can also keep higher chemical stability by the intermolecular force of itself, conducive to it is long when drillng operation.
According to the present invention, the specific example of the alkylidene of the C3-C10 for example may include: the Asia of the alkylidene of C3, C4
Alkyl, the alkylidene of C5, the alkylidene of C6, the alkylidene of C7, the alkylidene of C8, the alkylidene of C9, C10 alkylidene；C3-C8
Alkylidene the selection of adaptability can be carried out from above-mentioned specific example.
The specific example of the alkyl of the C1-C6 for example may include: the alkyl of C1, the alkyl of C2, the alkyl of C3, C4
Alkyl, the alkyl of C5, C6 alkyl；The alkyl of C1-C4 can carry out the selection of adaptability from above-mentioned specific example.
The specific example of halogen for example may include: F, Cl, Br, I.
According to the present invention, in order to obtain the more excellent shale control agent of performance, it is preferable that each R1It selects each independently
From the alkyl of C1-C4；R2The alkylidene of the C3-C8 replaced selected from hydroxyl.
It is highly preferred that each R1It is each independently selected from methyl, ethyl, n-propyl, isopropyl and normal-butyl；X is Cl, Br
Or I；R2Selected from-CH2-CH(OH)-CH2-、-CH2-CH2-CH(OH)-、 -CH(OH)-CH2-CH2-、-CH2-CH2-CH(OH)-
CH2-、-CH2-CH(OH)-CH2-CH2Or-CH2-CH2-CH(OH)-CH2-CH2-。
Wherein, structural unit shown in formula (1) can be selected from specific structure unit shown in following formula:
Formula (1-1): in formula (1), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-；
Formula (1-2): in formula (1), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-；
Formula (1-3): in formula (1), R1It is methyl, X Cl, R2Selected from-CH (OH)-CH2-CH2-；
Formula (1-4): in formula (1), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-；
Formula (1-5): in formula (1), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2-；
Formula (1-6): in formula (1), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2-；
Formula (1-7): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-；
Formula (1-8): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-；
Formula (1-9): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH (OH)-CH2-CH2-；
Formula (1-10): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-；
Formula (1-11): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2-；
Formula (1-12): in formula (1), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2-；
Formula (1-13): in formula (1), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2-；
Formula (1-14): in formula (1), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-；
Formula (1-15): in formula (1), R1It is methyl, X Br, R2Selected from-CH (OH)-CH2-CH2-；
Formula (1-16): in formula (1), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-；
Formula (1-17): in formula (1), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2-；
Formula (1-18): in formula (1), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2-；
Formula (1-19): in formula (1), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2-；
Formula (1-20): in formula (1), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-；
Formula (1-21): in formula (1), R1It is ethyl, X Br, R2Selected from-CH (OH)-CH2-CH2-；
Formula (1-22): in formula (1), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-；
Formula (1-23): in formula (1), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2-；
Formula (1-24): in formula (1), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2-。
According to the present invention, in order to obtain the shale control agent for being more suitable for water-base drilling fluid, it is preferable that the histidine polymerization
The histidine degree of polymerization of main chain is 7-8.The degree of polymerization refers to the group on the histidine polymer main chain of the modified polyhistidyl of per molecule
The quantity of propylhomoserin structural unit, in general, the histidine polymer main chain is formed with the conventional dehydrating condensation of polyaminoacid, also because
This, is keyed between histidine structure unit with amide.It is understood that modification polyhistidyl of the invention is linear polymerization
Object.
In the case of, according to the invention it is preferred to, the content of structural unit shown in formula (1) is 20mol% or more, preferably
20-60mol%, more preferably 40-60mol%.The molar content is all histidine structure lists with histidine polymer main chain
On the basis of first total mole number, including histidine structure unit shown in the above-mentioned formula (1) for being connected with modified group.
Second aspect of the present invention provides the preparation method of above-mentioned modified polyhistidyl, this method comprises:
(1) under alkaline condition, histidine or its salt are subjected to dehydration condensation, obtain polyhistidyl；
(2) in aqueous solvent, formula (1 ') compound represented and polyhistidyl are subjected to haptoreaction；
Formula (1 ')
Y is halogen, preferably Cl, Br or I.
According to the present invention, above-mentioned formula (1 ') compound represented can the structural unit according to shown in above-mentioned formula (1) change
Property unit structure is suitably selected.
Wherein, formula (1 ') compound represented can be selected from following specific structure compounds represented:
Formula (1 ' -1): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2, Y be Cl (as
3- chlorine-2-hydroxyl hydroxypropyltrimonium chloride)；
Formula (1 ' -2): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2- CH (OH)-, Y be Cl (as
The chloro- 1- trimethyl ammonium chloride of 3-)；
Formula (1 ' -3): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH (OH)-CH2-CH2, Y be Cl (as
3- chloro-3-hydroxyl hydroxypropyltrimonium chloride)；
Formula (1 ' -4): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2, Y be Cl (i.e.
For 4- chlorine-2-hydroxyl butyl trimethyl ammonium chloride)；
Formula (1 ' -5): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Cl；
Formula (1 ' -6): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Cl；
Formula (1 ' -7): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -8): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2- CH (OH)-, Y Cl；
Formula (1 ' -9): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH (OH)-CH2-CH2, Y Cl；
Formula (1 ' -10): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -11): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Cl；
Formula (1 ' -12): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Cl；
Formula (1 ' -13): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -14): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2- CH (OH)-, Y Cl；
Formula (1 ' -15): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH (OH)-CH2-CH2, Y Cl；
Formula (1 ' -16): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -17): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Cl；
Formula (1 ' -18): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Cl；
Formula (1 ' -19): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -20): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2- CH (OH)-, Y Cl；
Formula (1 ' -21): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH (OH)-CH2-CH2, Y Cl；
Formula (1 ' -22): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Cl；
Formula (1 ' -23): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Cl；
Formula (1 ' -24): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Cl。
Formula (1 ' -25): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -26): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2- CH (OH)-, Y Br；
Formula (1 ' -27): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH (OH)-CH2-CH2, Y Br；
Formula (1 ' -28): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -29): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Br；
Formula (1 ' -30): in formula (1 '), R1It is methyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Br；
Formula (1 ' -31): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -32): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2- CH (OH)-, Y Br；
Formula (1 ' -33): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH (OH)-CH2-CH2, Y Br；
Formula (1 ' -34): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -35): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Br；
Formula (1 ' -36): in formula (1 '), R1It is ethyl, X Cl, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Br；
Formula (1 ' -37): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -38): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2- CH (OH)-, Y Br；
Formula (1 ' -39): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH (OH)-CH2-CH2, Y Br；
Formula (1 ' -40): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -41): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Br；
Formula (1 ' -42): in formula (1 '), R1It is methyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Br；
Formula (1 ' -43): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -44): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2- CH (OH)-, Y Br；
Formula (1 ' -45): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH (OH)-CH2-CH2, Y Br；
Formula (1 ' -46): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2, Y Br；
Formula (1 ' -47): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH(OH)-CH2-CH2, Y Br；
Formula (1 ' -48): in formula (1 '), R1It is ethyl, X Br, R2Selected from-CH2-CH2-CH(OH)-CH2-CH2, Y is
Br。
According to the present invention, the histidine or its salt can be one of histidine, histidine hydrochloride etc. or a variety of.
As long as can be as the histidine raw material for preparing polyhistidyl.
It according to the present invention,, will be so that spontaneous polycondensation, shape occur for histidine by the dehydration condensation in step (1)
At polyhistidyl chain, wherein the alkaline condition can be provided by alkali compounds, and such alkali compounds can be from a variety of energy
It enough provides and is selected in the compound of alkaline condition, it is preferable that the alkali compounds is sodium hydroxide, potassium hydroxide and hydrogen
One of lithia is a variety of.The alkali compounds can be provided in the form of its aqueous solution, for example, with concentration be 40-60 weight
The form for measuring the alkali compounds aqueous solution of % provides.The dosage of the alkali compounds aqueous solution can become in a wider range
It is dynamic, it is preferable that relative to the histidine or its salt of 100 parts by weight,
In the case of, according to the invention it is preferred to, the condition of the dehydration condensation includes: that temperature is 180-250 DEG C, excellent
It is selected as 200-230 DEG C；Time is 2-6h, preferably 3.5-6h.
According to the present invention, step (2) carries out step (1) resulting polyhistidyl and formula (1 ') compound represented anti-
It answers, the modified group provided by formula (1 ') compound represented can be connected on histidine structure unit, so that this hair
Contain the structural unit that modified group is connected with shown in formula (1) on the histidine polymer main chain of bright modification polyhistidyl.Its
In, the histidine or its salt and the consumption proportion of formula (1 ') compound represented can according to the present invention needed for modification it is poly-
Histidine is suitably adjusted, it is preferable that the molar ratio of the histidine or its salt and formula (1 ') compound represented is 1:
0.5-5, preferably 1:0.6-3, more preferably 1:1.01-2.55.
Wherein, the aqueous solvent can be water, or do not influence containing other reaction of the invention solvent it is water-soluble
Liquid.The dosage of the aqueous solvent can change in a wider range, it is preferable that described containing water-soluble relative to the histidine of 10g
The dosage of agent is 100-500mL, preferably 120-250mL.
According to the present invention it is possible to first the polyhistidyl is dissolved in the aqueous solvent, then shown in introduction-type (1 ')
Compound carry out haptoreaction.Preferably, alkali compounds can first be added in the aqueous solution of polyhistidyl, is re-introduced into
Formula (1 ') compound represented carries out haptoreaction, and the alkali compounds is as described in above, it is preferable that relative to 100
The histidine of parts by weight, the dosage of the alkali compounds are 5-20 parts by weight.
In the case of, according to the invention it is preferred to, the catalytic condition includes: that temperature is 45-80 DEG C, time 2-
15h。
Third aspect present invention provides above-mentioned modified polyhistidyl as supermolecule shale control agent in water-base drilling fluid
In application.
When above-mentioned modified polyhistidyl of the invention is used as supermolecule shale control agent in water-base drilling fluid, it will play excellent
Good shale inhibitory effect, and there is excellent heat-resisting property.
Fourth aspect present invention, which provides, a kind of contains above-mentioned modified polyhistidyl as the water base of supermolecule shale control agent
Drilling fluid.
According to the present invention, the supermolecule shale control agent can be obtained excellent shale at lower levels and inhibit
Effect, it is preferable that relative to the water in the water-base drilling fluid of 100 parts by weight, the content of the supermolecule shale control agent is 1-3
Parts by weight.
According to the present invention, other additives that the water-base drilling fluid can also routinely be used containing this field, for example, it is swollen
Moisten soil, tackifier, anti-sloughing agent, lubricant, heavy weight additive, alkaline conditioner etc., the type and content of these additives can be
The type and content that this field routinely uses, there is no particular limitation to this by the present invention.
Fifth aspect present invention puts on the application for stating water-base drilling fluid in oil/gas drilling.
When drilling fluid provided by the present invention to be applied in oil/gas drilling, shale expansion, table can be effectively inhibited
Reveal excellent inhibitory effect, and there is good high temperature inhibitory effect.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is for illustrating modification polyhistidyl and preparation method thereof of the invention.
(1) 10g histidine hydrochloride is weighed in culture dish, adds the NaOH aqueous solution that 4g concentration is 50 weight %；
It is subsequently placed in Muffle furnace, and reacts 4h after being warming up to 200 DEG C, and is primary every half an hour stirring, polyhistidyl is obtained, through reflecting
Its fixed histidine degree of polymerization is 7；
(2) gained polyhistidyl is dissolved in 150mL water, adds 1.0g NaOH；Then the chloro- 2- of 3- of 10g is weighed
Hydroxypropyl-trimethyl ammonium chloride is added in polyhistidyl solution, stirs evenly；6h is reacted after being warming up to 50 DEG C；By products therefrom
Supermolecule inhibitor SI-1 is obtained after drying and grinding, identifies that quaternary ammonium salt group contained by the supermolecule inhibitor is 41mol%.
Embodiment 2
The present embodiment is for illustrating modification polyhistidyl and preparation method thereof of the invention.
(1) 10g histidine hydrochloride is weighed in culture dish, adds the NaOH aqueous solution that 4g concentration is 50 weight %；
It is subsequently placed in Muffle furnace, and reacts 3.5h after being warming up to 220 DEG C, and is primary every half an hour stirring, obtain polyhistidyl, pass through
Identify that its histidine degree of polymerization is 8；
(2) gained polyhistidyl is dissolved in 150mL water, adds 1.0g NaOH；Then the chloro- 2- of 3- of 25g is weighed
Hydroxypropyl-trimethyl ammonium chloride is added in polyhistidyl solution, stirs evenly；8h is reacted after being warming up to 65 DEG C；Products therefrom is done
Supermolecule inhibitor SI-2 is obtained after dry grinding, quaternary ammonium salt group contained by the identified supermolecule inhibitor is 56mol%.
Embodiment 3
The present embodiment is for illustrating modification polyhistidyl and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, in step (1), the reaction condition in Muffle furnace is different, i.e.,
4h is reacted after being warming up to 250 DEG C, to obtain the polyhistidyl that the histidine degree of polymerization is 9, step (2) is eventually passed through and obtains oversubscription
Sub- inhibitor SI-3.
Embodiment 4
The present embodiment is for illustrating modification polyhistidyl and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, in step (1), the reaction condition in Muffle furnace is different, i.e.,
3.5h is reacted after being warming up to 180 DEG C, to obtain the polyhistidyl that the histidine degree of polymerization is 6, step (2) is eventually passed through and is surpassed
Molecule inhibitor SI-4.
Embodiment 5
The present embodiment is for illustrating modification polyhistidyl and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, in step (2), 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride
Dosage is 5g, eventually passes through step (2) and obtains supermolecule inhibitor SI-5, quaternary ammonium salt base contained by the identified supermolecule inhibitor
Group is 22mol%.
Comparative example 1
According to method described in embodiment 1, the difference is that, in step (1), the reaction condition in Muffle furnace is different, i.e.,
4h is reacted after being warming up to 280 DEG C, to obtain the polyhistidyl that the histidine degree of polymerization is 12, step (2) is eventually passed through and is surpassed
Molecule inhibitor DSI-1.
Comparative example 2
According to method described in embodiment 1, the difference is that, in step (1), the reaction condition in Muffle furnace is different, i.e.,
4h is reacted after being warming up to 150 DEG C, to obtain the polyhistidyl that the histidine degree of polymerization is 4, step (2) is eventually passed through and obtains oversubscription
Sub- inhibitor DSI-2.
Test case 1
Above-mentioned inhibitor, potassium chloride, polyetheramine (being purchased from Ann Kyrgyzstan company, analyze pure) are prepared into 1 weight %'s respectively
Aqueous solution utilizes page by acquired solution and clear water according to professional standard (SY/T 6335-1997) shale inhibition evaluation method
The expansion height for 24 hours of the artificial compacting bentonite in lump of rock dilatometer measurement, evaluates the inhibition of inhibitor, as a result such as 1 institute of table
Show.
Table 1
As the data of table 1 can be seen that by means of the present invention made from modified polyhistidyl can be in water base brill
Excellent shale inhibitory effect is played in well liquid.
Test case 2
Shale landwaste 20g (crossing 6-10 mesh screen) is taken, the aqueous solution and clear water of 2 weight % inhibitor are respectively put into
In, inhibitor here refers to the inhibitor and potassium chloride being obtained above, polyetheramine (purchased from Ann Kyrgyzstan company, analysis
It is pure)；Then it is placed in heat rolling 16h in 120 or 150 DEG C in ageing can, the landwaste in the inhibitor solution after heat rolling is crossed into 40 mesh
Sieve, the landwaste that will be left on sieve dry and weigh its quality (m1), rolling rate of recovery (R) can calculate according to the following formula:
Rolling rate of recovery (R)=(m1/ 20) × 100%, the results are shown in Table 2.
Table 2
| Prepare liquid | 120 DEG C of rolling rate of recoveries (%) | 150 DEG C of rolling rate of recoveries (%) |
| Clear water | 26.5 | 23.6 |
| SI-1 | 92.3 | 90.1 |
| SI-2 | 97.7 | 96.2 |
| SI-3 | 73.6 | 65.8 |
| SI-4 | 86.2 | 80.1 |
| SI-5 | 68.4 | 52.1 |
| DSI-1 | 38.3 | 26.8 |
| DSI-2 | 42.5 | 29.3 |
| Potassium chloride | 35.4 | 30.9 |
| Polyetheramine | 78.2 | 74.3 |
Can be seen that made from method of the invention modified polyhistidyl as the data of table 2 can be in water-base drilling fluid
Good temperature resistance is shown when middle conduct shale control agent.
Test case 3
By the inhibitor being obtained above with being added in 4 weight % clay solution, so that the content of inhibitor is 0.5 weight
Measuring % makes it be uniformly dispersed mixed solution sonic oscillation 20min, and utilizes zeta potential instrument and micron granularity distribution instrument
Inhibitor is tested to the Zeta potential and particle diameter distribution of clay, the results are shown in Table 3.
Table 3
It can be seen from Table 3 that modified polyhistidyl made from method of the invention can pass through as shale control agent
Electrostatic force declines its Zeta potential in clay particle surface absorption, so that the dispersibility of clay particle weakens, reaches suppression
The effect of swelling wall rock hydration swelling processed, to control the aquation dispersion of shale.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of modification polyhistidyl for being suitable for supermolecule shale control agent, which is characterized in that the group of the modification polyhistidyl
Contain the structural unit that modified group is connected with shown in formula (1) on propylhomoserin polymer main chain；
The histidine degree of polymerization of the histidine polymer main chain is 6-9；
Each R1It is each independently selected from the alkyl of C1-C6；X is selected from halogen；R2The alkylidene of the C3-C10 replaced selected from hydroxyl.
2. modified polyhistidyl according to claim 1, wherein each R1It is each independently selected from the alkyl of C1-C4；R2
The alkylidene of the C3-C8 replaced selected from hydroxyl；
Preferably, each R1It is each independently selected from methyl, ethyl, n-propyl, isopropyl and normal-butyl；X is Cl, Br or I；R2
Selected from-CH2-CH(OH)-CH2-、-CH2-CH2-CH(OH)-、-CH(OH)-CH2-CH2-、-CH2-CH2-CH(OH)-CH2-、-
CH2-CH(OH)-CH2-CH2Or-CH2-CH2-CH(OH)-CH2-CH2-。
3. modified polyhistidyl according to claim 1 or 2, wherein the histidine of the histidine polymer main chain polymerize
Degree is 7-8.
4. modification polyhistidyl described in any one of -3 according to claim 1, wherein structural unit shown in formula (1)
Content is 20mol% or more, preferably 20-60mol%, more preferably 40-60mol%.
5. the preparation method of modification polyhistidyl described in any one of claim 1-4, this method comprises:
(1) under alkaline condition, histidine or its salt are subjected to dehydration condensation, obtain polyhistidyl；
(2) in aqueous solvent, formula (1 ') compound represented and polyhistidyl are subjected to haptoreaction；
Y is halogen, preferably Cl, Br or I.
6. according to the method described in claim 5, wherein, mole of the histidine or its salt and formula (1 ') compound represented
Than for 1:0.5-5, preferably 1:0.6-3, more preferably 1:1.01-2.55.
7. according to the method described in claim 6, wherein, the condition of the dehydration condensation includes: that temperature is 180-250
DEG C, time 2-6h；
Preferably, it is 45-80 DEG C that the catalytic condition, which includes: temperature, time 2-15h.
8. modification polyhistidyl described in any one of claim 1-4 is as supermolecule shale control agent in water-base drilling fluid
In application.
9. a kind of contain water of the modification polyhistidyl as supermolecule shale control agent described in any one of claim 1-4
Base drilling fluid.
10. application of the water-base drilling fluid as claimed in claim 9 in oil/gas drilling.
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