CN106336467A - Modified chitosan, preparation method thereof, application of chitosan as shale inhibitor, drilling fluid and application thereof - Google Patents
Modified chitosan, preparation method thereof, application of chitosan as shale inhibitor, drilling fluid and application thereof Download PDFInfo
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- CN106336467A CN106336467A CN201610726240.9A CN201610726240A CN106336467A CN 106336467 A CN106336467 A CN 106336467A CN 201610726240 A CN201610726240 A CN 201610726240A CN 106336467 A CN106336467 A CN 106336467A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- 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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Abstract
The invention relates to the field of drilling in the petroleum industry, in particular to modified chitosan, a preparation method thereof, application of chitosan as a shale inhibitor, drilling fluid and application thereof. The modified chitosan has a modified group shown in the formula (1). The modified chitosan is adopted as the shale inhibitor to be applied to oil gas drilling, and particularly shale gas drilling, the good inhibition effect can be obtained, the modified chitosan has the good temperature resistance and can keep the high inhibition effect under the high temperature for a long time, and the modified chitosan has the biodegradability, and can be adopted as the environmentally friendly shale inhibitor.
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of modification of chitosan and preparation method thereof and
Application as shale control agent and drilling fluid and its application.
Background technology
With the raising of human living standard, the mankind are growing to the consumption of the energy.The exploitation of traditional conventional energy resource is difficult
To meet the consumer need of people.The exploration and development of the unconventional resource such as shale gas is more and more important.The business of U.S.'s shale gas
The exploitation changed, the exploitation upsurge of the very big unconventional energy resource having driven the whole world.In the recent period, domestic also great attention shale gas etc. are non-
The exploitation of conventional energy resource.The exploitation about 70% application oil base drilling fluid of external shale gas and 30% water-based drilling fluid at present,
Then domestic almost all application oil base drilling fluid.There is Heavy environmental pollution problem in the application of oil base drilling fluid.Environmental problem
Cause the attention of various countries, oil base drilling fluid is possible to face disabled danger, therefore water-based drilling in following application
Liquid is the developing direction of following drilling fluid.
Shale be a kind of sedimentary rock, matter rigid crisp, permeability is low, nano-micron pore gap develop abundant.Shale gas are enriched with a large number
In shale.In drilling process, on the one hand because the clay mineral of oil-gas Layer occurs hydration swelling, dispersion migration, corrosion to divide
Dissipate, thus reservoir is caused with the injury of unrepairable；On the other hand, drilling fluid enters oil-gas Layer and will result in water lock, emulsifying, moistening
Reversion and chemical precipitation.For the accumulation feature of shale, traditional mining type cannot meet the exploitation of shale gas.Shale gas
Exploitation is based on shallow-layer extended reach well, cluster horizontal well well spacing.Developed due to the nano-micron pore gap of shale and enrich, in long horizontal sections
Drilling process it is easy to lead to leakage, cave in, the drilling problem such as undergauge, bit freezing, Wellbore Stability becomes restriction water-base drilling fluid
The bottleneck of development.
It is ensured that the wellbore stability of shale it is critical only that raising drilling fluid rejection ability for water-base drilling fluid.Wherein,
Inhibitor is a kind of additive of the first-selected rejection ability of raising water-base drilling fluid.At present, inhibitor has a lot of industrial products,
The shale control agent great majority using both at home and abroad are polyamine class shale control agent, and it has, and inhibition is good, low toxicity, compatibility
Good, but its temperature resistant capability is poor；And other shale inhibitions with the shale control agent of temperature resistant capability are poor, during suppression
Between shorter, and the polymer being mostly not easily decomposed.
Content of the invention
It is an object of the invention to overcoming existing shale control agent to be difficult to have good inhibition and heat resistance concurrently
Defect, provide a kind of having good inhibition and heat resistance concurrently and modification of chitosan of environmental protection and preparation method thereof and
Application as shale control agent and drilling fluid and its application.
To achieve these goals, the present invention provides a kind of modification of chitosan, and described modification of chitosan has following formula (1) institute
The modified group shown:
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
Present invention also offers a kind of preparation method of modification of chitosan, the method includes:
(1) in the presence of alkali compoundss, in a solvent, shitosan is carried out basification；
(2) by the product after described basification and provide the modified group shown in following formula (1) ammonium salt carry out quaternized
Reaction,
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
Present invention also offers the modification of chitosan being obtained by said method.
Present invention also offers by above-mentioned modification of chitosan as the shale control agent in drilling fluid in oil/gas drilling
Application.
Present invention also offers a kind of containing above-mentioned modification of chitosan as shale control agent water-base drilling fluid.
Present invention also offers application in oil/gas drilling for the above-mentioned water-base drilling fluid.
Above-mentioned modification of chitosan is applied in oil/gas drilling by the present invention as shale control agent, particularly shale gas drilling well
In, it is obtained in that excellent inhibition, and this modification of chitosan has good heat resistance, can be for a long time higher
At a temperature of keep higher inhibitory action, and this modification of chitosan has the biodegradable of shitosan, belongs to environment
The shale control agent of friendly.Therefore, can be in high temperature page by shale control agent is used as using the modification of chitosan of the present invention
The aquation of shale can be suppressed in rock drilling process well to disperse, expand migration etc., and will not be to environment.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Herein the end points of disclosed scope and any value are not limited to this accurate scope or value, these scopes or
Value should be understood to comprise the value close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively
Between the endpoint value of individual scope and single point value, and can be obtained one or more between single point value with combination with one another
New numerical range, these numerical rangies should be considered herein specifically to disclose.
In the present invention, shale control agent refers in drilling process, in the higher layer in brill chance rammell and clay mineral content
Duan Shi, due to the characteristic of clay easily aquation, expansion, dispersion, migration itself, often results in the borehole well instability in drilling process, collapses
The problems such as collapse, and shale control agent is exactly to stop shale and clay mineral hydration swelling by Electrostatic Absorption and ion exchange, prevents
The only chemical reagent of cave-in.
The present invention provides a kind of modification of chitosan, and described modification of chitosan has a modified group shown in following formula (1):
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
According to the present invention, above-mentioned modification of chitosan is connected with the modified group shown in following formula (1), particularly forms following formula
(2) in the case of the construction unit shown in, using in the shale control agent as drilling fluid, by Electrostatic Absorption and ion exchange
Stop hydration swelling and the dispersion migration of clay mineral, thus preventing the generation of borehole well instability and the problem of caving in.Especially for
For shale gas drilling well, the modification of chitosan of the present invention is particularly well suited as the shale control agent of shale gas drilling well, in page
During rock pneumatic drill well, the modification of chitosan main chain of the present invention has adsorption group, and side chain has more cation groups,
So, modification of chitosan in aqueous on the one hand due to after its protonation reaction positively charged thus absorption is in shale surface, according to
By the strong absorption of electrostatic interaction in shale surface, weaken electrostatic repulsion and the surface hydration film repulsion of shale surface；On the other hand, change
Substantial amounts of adsorption group on property shitosan, can be in shale surface multipoint adsorption simultaneously, thus shale is tightly strapped in one
Rise, stop its hydration swelling.Additionally, the anion of cation group on modification of chitosan and shale surface is made by electrostatic
With also preventing the hydration swelling of shale further:
Formula (2)
That is it is preferable that described modification of chitosan has the construction unit shown in above-mentioned formula (2).Although above-mentioned formula
(2) ratio that the construction unit shown in accounts for whole modification of chitosan can change in relative broad range, but is able to more preferably
Ground plays above-mentioned modification of chitosan as inhibition during shale control agent and heat resistance it is preferable that with described modification
On the basis of shitosan gross weight, the content of the construction unit shown in described formula (2) is more than 40 weight %, preferably 50-90 weight
Amount %, more preferably 60-85 weight %, still more preferably for 65-80 weight %.
In the present invention, the alkyl of above-mentioned c1-c8 can be for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl etc..
The alkylidene of above-mentioned c1-c8 can be the alkylidene that formed of alkyl of above-mentioned c1-c8.
Under preferable case, r1-r3It is each independently selected from the alkyl of c1-c6, r4And r5It is each independently selected from c1-c6's
Alkylidene.
It is highly preferred that r1-r3It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl, r4And r5Each
Independently selected from-ch2-、-ch2-ch2-、-ch2-ch2-ch2-、-ch(ch3)-ch2-、-ch2-ch(ch3)-and-ch2-(ch2)2-
ch2-.
In the preferred embodiment of the present invention, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5Selected from-
ch2-.
In another kind of preferred implementation of the present invention, r1-r3Selected from ethyl, r4It is selected from-ch2-ch2-ch2-, r5Choosing
From-ch2-.
In another kind of preferred implementation of the present invention, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5Choosing
From-ch2-ch2-.
In another kind of preferred implementation of the present invention, r1-r3Selected from ethyl, r4It is selected from-ch2-ch2-ch2-, r5Choosing
From-ch2-ch2-.
In the preferred embodiment of the present invention, r1-r3Selected from methyl, r4It is selected from-ch2-(ch2)2-ch2-, r5Choosing
From-ch2-.
In another kind of preferred implementation of the present invention, r1-r3Selected from ethyl, r4It is selected from-ch2-(ch2)2-ch2-, r5Choosing
From-ch2-.
According to the present invention, although the molecular weight of above-mentioned modification of chitosan can change in wider scope, it is in order at
The compatibility being suitable to water-base drilling fluid considers, under preferable case, the number-average molecular weight of described modification of chitosan is 20000-80000,
It is preferably 40000-70000, more preferably 50000-60000.
In terms of the invention, it is understood that the modified group shown in formula (1) carries positive charge, for this, it can form ammonium
Salt structure, thus with certain anion.For this reason, the present invention is to this anion, and there is no particular limitation, can be conventional ammonium
Anion in salt, for example, can be selected from cl-、br-、i-One or more of Deng.
Present invention also offers a kind of preparation method of modification of chitosan, the method includes:
(1) in the presence of alkali compoundss, in a solvent, shitosan is carried out basification；
(2) by the product after described basification and provide the modified group shown in following formula (1) ammonium salt carry out quaternized
Reaction,
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
According to the present invention, although the present invention can be obtained as long as being prepared according to the preparation method of above-mentioned modification of chitosan
Required can be used as the product of shale control agent, and especially said method will be obtained modification of chitosan described above,
I.e. the modification of chitosan of the method gained has the modified group shown in formula (1).As described above it is preferable that described
Modification of chitosan has the construction unit shown in following formula (2).And, the specific descriptions of each group therein are also as above institute
Description, will not be described here.
In the preparation method of above-mentioned modification of chitosan, in step (1), shitosan is carried out basification, enables to shell
Polysaccharide is easier to dissociate ammonium root group such that it is able to carry out described quaterisation in step (2).Wherein, described alkalescence
Compound can be using the conventional compound that shitosan Ji can be carried out with basification in this area, such as Feldalat NM, methanol
One or more of potassium, Sodium ethylate, potassium ethoxide, sodium tert-butoxide, sodium hydroxide, potassium hydroxide and Lithium hydrate etc., preferably
One or more of sodium hydroxide, potassium hydroxide and Lithium hydrate, particularly preferably sodium hydroxide.It is suitable in order to obtain
The shitosan of described quaterisation it is preferable that with respect to 100 weight portions shitosan, described alkali compoundss are (with dry weight
Meter) consumption be 2-8 weight portion, preferably 3-5 weight portion.Above-mentioned alkali compoundss can introduce in solid form it is also possible to
Introduce as a solution, it is preferred to use the form of solution, for example with the form of the aqueous solution for 50-70 weight % for the concentration.
According to the present invention, the selection of wherein said shitosan can be selected according to required modification of chitosan, for example
It is that (preferably 40000-70000, still more preferably for 50000- for 20000-80000 needing to prepare number-average molecular weight
60000), during modification of chitosan, the number-average molecular weight of preferably described shitosan is 15000-80000, more preferably 20000-
60000, still more preferably for 30000-40000.
According to the present invention, this basification will be carried out in a solvent, so that shitosan is at preferable dissolved form
State and the contact between alkali compoundss is also more abundant.Preferably, described solvent is isopropanol, methanol, ethanol and propanol
One or more of, the dissolving of shitosan can be conducive to using such solvent, the quaterisation after being also suitably for
Carry out.Under preferable case, with respect to the shitosan of 100 weight portions, the consumption of described solvent is 800-2000 weight portion, preferably
900-1500 weight portion.
According to the present invention, in order to substantially more reach the purpose of alkalization shitosan, above-mentioned steps (1) preferably first will
Shitosan is mixed with solvent, preferably to form the solution of shitosan, is re-introduced into alkali compoundss and carries out basification.Preferably feelings
Under condition, the condition of described basification includes: temperature is 40-70 DEG C (preferably 45-60 DEG C), and the time is 2-8h (preferably 3-
5h).
According to the present invention, in step (2), by above-mentioned alkalinization, on the one hand system is also made to maintain certain alkali
Property environment, in this case, introduce provide described modified group ammonium salt carry out quaterisation, you can make shitosan
Connect the modified group shown in above formula (1), thus obtaining the modification of chitosan containing the construction unit shown in formula (2).
Wherein, the ammonium salt providing described modified group can be according to above selecting to the specific descriptions of modified group
Select it is preferable that described ammonium salt is the compound shown in formula (3):
Formula (3)Wherein, x can be for example
Cl, br, i etc., l-Anion can be the various aniones entrained by ammonium salt, for example, can be cl-、br-、i-Deng.
The present invention one kind preferred embodiment in, in step (2), described ammonium salt be (3- (2- chloromethyl) propylene
Acylamino-) hydroxypropyltrimonium chloride (namely in compound shown in formula (3), r1-r3Selected from methyl, r4It is selected from-ch2-ch2-
ch2-, r5It is selected from-ch2-, x is cl, l-For cl-), (3- (2- chloromethyl) acrylamido) propyl group triethyl ammonium chloride (namely formula
(3) in compound shown in, r1-r3Selected from ethyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-, x is cl, l-For cl-)、(3-
(2- chloroethyl) acrylamido) hydroxypropyltrimonium chloride (namely in compound shown in formula (3), r1-r3Selected from methyl, r4Choosing
From-ch2-ch2-ch2-, r5It is selected from-ch2-ch2-, x is cl, l-For cl-), (3- (2- chloroethyl) acrylamido) propyl group three second
Ammonium chloride (namely in compound shown in formula (3), r1-r3Selected from ethyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-
ch2-, x is cl, l-For cl-), (4- (2- chloromethyl) acrylamido) butyl trimethyl ammonium chloride (namely chemical combination shown in formula (3)
In thing, r1-r3Selected from methyl, r4It is selected from-ch2-(ch2)2-ch2-, r5It is selected from-ch2-, x is cl, l-For cl-) and (4- (2- chloromethane
Base) acrylamido) butyl triethyl ammonium chloride (namely in compound shown in formula (3), r1-r3Selected from ethyl, r4It is selected from-ch2-
(ch2)2-ch2-, r5It is selected from-ch2-, x is cl, l-For cl-One or more of).
In order to make to connect upper appropriate modified group on shitosan, particularly obtaining content is more than 40 weight %
Shown in the formula (2) of (preferably 50-90 weight %, more preferably 60-85 weight %, still more preferably for 65-80 weight %)
Construction unit it is preferable that in step (2), with respect to the shitosan of 100 weight portions, the consumption of described ammonium salt is 40-200 weight
Amount part, preferably 80-150 weight portion, more preferably 100-120 weight portion.Wherein, described ammonium salt can carry in solid form
For it is also possible to provide it is preferable that described ammonium salt carries in the form of concentration is for the aqueous solution of 60-70 weight % as a solution
For.
According to the present invention, in above-mentioned steps (2), in order to make described quaterisation more successfully carry out, excellent
After product after described basification is first mixed by choosing with the ammonium salt providing described modified group, carry out described quaternized instead
Should.Wherein, the condition of this mixing preferably includes: temperature is 40-70 DEG C (preferably 45-60 DEG C), and the time is for 10-40min (preferably
For 20-30min).Preferably, the condition of described quaterisation includes: temperature is 65-90 DEG C (preferably 70-80 DEG C), the time
For 2-6h (preferably 3.5-5h).
According to the present invention, in order to extract the modification of chitosan of gained, the preparation side of above-mentioned modification of chitosan
Method can also include, and the product after quaterisation is neutralized, solid-liquid separation (mode for example with sucking filtration is carried out), washes
Wash solid phase (being washed using above-mentioned solvent, washing times can be 2-5 time) and be dried.Wherein, neutralization makes the anti-of gained
The ph answering system between 6.5-7.5, particularly in 7-7.5.For example can be neutralized using hydrochloric acid.Wherein, it is dried
Condition for example may include that temperature is 80-100 DEG C, the time be 20-48h.
Present invention also offers the modification of chitosan being obtained by said method.As long as this modification of chitosan passes through said method
It is obtained and is present invention modification of chitosan required here, but description specifically still may refer to above to modified shell
The description of polysaccharide.
Present invention also offers by above-mentioned modification of chitosan as the shale control agent in drilling fluid in oil/gas drilling
Application.According to the present invention, described modification of chitosan is used for as shale control agent in water-base drilling fluid, by the water base brill of gained
Well liquid is used for the application of oil/gas drilling, particularly in high temperature shale drilling process, you can obtain preferable inhibition.
Present invention also offers a kind of containing above-mentioned modification of chitosan as shale control agent water-base drilling fluid.As above institute
Description, according to the present invention, described modification of chitosan is used for as shale control agent in water-base drilling fluid, gained is water base
Drilling fluid is used for the application of oil/gas drilling, particularly in high temperature shale drilling process, you can obtain preferable inhibition, page processed
The aquation dispersion of rock, expansion migration etc., and will not be to environment.Preferably, described oil/gas drilling is shale pneumatic drill
Well, as above, the drilling fluid with described modification of chitosan is particularly well-suited to shale gas drilling well.
According to the present invention, the consumption of described modification of chitosan can select the routine of shale control agent in water-base drilling fluid
Consumption is it is preferable that with respect to the water in the described water-base drilling fluid of 100 weight portions, the consumption of described modification of chitosan is 1-3 weight
Amount part.
According to the present invention, there is no particular limitation to the water base drilling fluid system containing modification of chitosan for the present invention, permissible
For the conventional various water base drilling fluid system in this area, as long as being added into the present invention in these conventional water base drilling fluid system
Modification of chitosan.Can be for example potassium chloride-polyglycol drilling fluid, organosilicon as such conventional drilling liquid system
One or more of drilling fluid and cationic drilling fluid.Described potassium chloride-polyglycol drilling fluid can be people in the art
Various potassium chloride-polyglycol drilling fluid known to member, for example, can be potassium chloride-PEG drilling fluid, potassium chloride-poly- third
Glycol drilling fluid, potassium chloride-ethylene glycol/propylene glycol copolymers drilling fluid, potassium chloride-polyglycerol drilling fluid and potassium chloride-poly-
One or more of ethylene glycol drilling fluid；It is each that described silicone drilling fluid can be well known to those skilled in the art
Plant silicone drilling fluid, the organosilicon in described silicone drilling fluid can be selected from methyl silicon sodium alcoholate, methyl silanol potassium and to have
One or more of machine silicon potassium humate.The various sun that described cationic drilling fluid can be well known to those skilled in the art
Ion drilling fluid, the cation in described cationic drilling fluid can be chloro- selected from 2,3- epoxypropyltrimethylchloride chloride, 3-
One or more of 2- hydroxypropyl-trimethyl ammonium chloride and PAMC.
Normally, other additives as water-base drilling fluid, preferable case can also be contained in described water-base drilling fluid
Under, the drilling fluid of the present invention contains one of bentonite, viscosifier, anti-sloughing agent, fluid loss additive, lubricant and heavy weight additive or many
Kind.
Wherein, described bentonite refers to the clay with montmorillonite as main mineral constituent, and it has, and imparting drilling fluid is viscous to be cut
Power and the effect of leak-off wave making machine, for example, can be sodium bentonite and/or calcium-base bentonite, preferably sodium bentonite.More
Preferably, with respect to the water in the described water-base drilling fluid of 100 weight portions, described bentonitic content is 2-6 weight portion, more excellent
Elect 3-5 weight portion as.
Wherein, described viscosifier can improve the viscous shear force of drilling fluid, for example, can be polyacrylamide potassium salt (kpam), gather
One of copolymer (the such as trade mark is 80a51) of anionic cellulose (such as pac141) and acrylamide and sodium acrylate
Or multiple, preferably polyacrylamide potassium salt.It is highly preferred that with respect to the water in the described water-base drilling fluid of 100 weight portions, institute
The content stating viscosifier is 0.3-1 weight portion, more preferably 0.4-0.8 weight portion.
Wherein, described anti-sloughing agent can assist bionical shale control agent to prevent hole collapse, to improve borehole wall stability, example
As being in potassium humate (khm), organosilicon (the such as trade mark is gf-1) and sulfonated gilsonite (the such as trade mark is ft-1a)
Plant or multiple, preferably potassium humate.It is highly preferred that with respect to the water in the described water-base drilling fluid of 100 weight portions, described anti-
Collapse agent content be 1-3 weight portion.
Wherein, described fluid loss additive can improve wellbore liquid leaching loss wave making machine, for example, can be sulfonated-pheno-formoldehyde resin (example
If the trade mark is smp-i, smp-ii), in sulfonated-methyl brown coal resin (such as the trade mark be spnh) and amphoteric ion polymer jt-888
One or more, preferably smp-ii and/or spnh.It is highly preferred that with respect in the described water-base drilling fluid of 100 weight portions
Water, the content of described fluid loss additive is 1-3 weight portion, more preferably 1.5-2 weight portion.
Wherein, described wetting agent can improve drilling fluid lubricating performance, prevents the down-hole such as bit freezing complicated state, for example permissible
For sulfonation oil foot (the such as trade mark is fk-10), diesel oil and surfactant mixture (if the trade mark is frh) and fatty glyceride
With one or more of surfactant mixture (if the trade mark is fk-1), modified phospholipid.It is highly preferred that with respect to 100 weights
Water in the described water-base drilling fluid of amount part, the content of described lubricant is 0.5-2 weight portion.
Wherein, the density acting as adjusting drilling fluid of described heavy weight additive reaches desired density, for example, can be barite
(can be for example barite more than 90 weight % for the barium sulfate content), organic salt (weigh-1, weigh-2 (active component
For potassium formate), weigh-3, Organic Sodium Salt gd-wt) etc. one or more of.Described drilling fluid with respect to 100 weight portions
In water it is preferable that described heavy weight additive content be 200-400 weight portion, more preferably 330-350 weight portion.
The various materials that above-mentioned additive is can be commercially available product it is also possible to be obtained according to the conventional method in this area, this
In repeat no more.
Present invention also offers application in oil/gas drilling for the above-mentioned water-base drilling fluid.
According to the present invention, can be in high temperature shale drilling well by shale control agent is used as using the modification of chitosan of the present invention
During the aquation of shale can be suppressed well to disperse, expand migration etc., and will not be to environment.
Hereinafter will be described the present invention by embodiment.
In following preparation example and comparative example:
Number-average molecular weight is that (experimental apparatus are the gel permeation chrommatograph of waters company of the U.S., model using gpc gel chromatography
For e2695) measure.
The content of the construction unit shown in formula (2) refers to that the middle content of the construction unit shown in formula (2) accounts for entirely modified shell
The percentage by weight of polysaccharide.
Embodiment 1
The present embodiment is used for modification of chitosan of the present invention and preparation method thereof is described.
(1) by the shitosan of 100g, (purchased from thyrite Chemical Co., Ltd. of Huantai County, number-average molecular weight is 35000, below
With) be dissolved in the isopropanol of 1300g, (this concentration of aqueous solution is 60 weight %, and consumption makes to be subsequently adding sodium hydrate aqueous solution
The addition of sodium hydroxide is 4g), and basification 4h at 60 DEG C；
(2) continue, at 60 DEG C, in the system after above-mentioned basification, to add (3- (2- chloromethyl) acrylamido)
(this concentration of aqueous solution is 65 to the aqueous solution of hydroxypropyltrimonium chloride (purchased from thyrite Chemical Co., Ltd. of Huantai County, as follows)
Weight %, it is 100g that consumption makes the addition of (3- (2- chloromethyl) acrylamido) hydroxypropyltrimonium chloride), and stir
Mixing 30min；At 80 DEG C, then carry out quaterisation 4h；
(3) product after above-mentioned quaterisation is cooled to room temperature, and ph to 7 is adjusted using hydrochloric acid；Then sucking filtration, uses
Isopropanol washing filter cake 3 times, and filter cake is placed in 80 DEG C of vacuum drying ovens 24h is dried, obtain the solid of 200g, this solid is
For modification of chitosan c1.
Through infrared, proton nmr spectra and the detection of carbon analysis of spectrum, there is in this modification of chitosan the structure list shown in formula (2)
First (wherein, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-), and content is 80 weight %；This modified shell
The number-average molecular weight of polysaccharide is 58000.
Embodiment 2
The present embodiment is used for modification of chitosan of the present invention and preparation method thereof is described.
(1) shitosan of 100g is dissolved in the propanol of 1000g, (this aqueous solution is dense to be subsequently adding sodium hydrate aqueous solution
Spend for 65 weight %, it is 4g that consumption makes the addition of sodium hydroxide), and basification 3.5h at 55 DEG C；
(2) continue, at 55 DEG C, in the system after above-mentioned basification, to add (3- (2- chloromethyl) acrylamido)
(this concentration of aqueous solution is 65 weight % to the aqueous solution of hydroxypropyltrimonium chloride, and consumption makes epoxypropyltrimethylchloride chloride
Addition be 100g), and stir mixing 30min；At 75 DEG C, then carry out quaterisation 5h；
(3) product after above-mentioned quaterisation is cooled to room temperature, and ph to 7 is adjusted using hydrochloric acid；Then sucking filtration, uses
Propanol rinse filter cake 3 times, and filter cake is placed in 90 DEG C of vacuum drying ovens 24h is dried, obtain the solid of 200g, this solid is
Modification of chitosan c2.
Through infrared, proton nmr spectra and the detection of carbon analysis of spectrum, there is in this modification of chitosan the structure list shown in formula (2)
First (wherein, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-), and content is 68 weight %；This modified shell
The number-average molecular weight of polysaccharide is 50000.
Embodiment 3
The present embodiment is used for modification of chitosan of the present invention and preparation method thereof is described.
(1) shitosan of 100g is dissolved in the isopropanol of 950g, (this aqueous solution is dense to be subsequently adding sodium hydrate aqueous solution
Spend for 60 weight %, it is 5g that consumption makes the addition of sodium hydroxide), and basification 5h at 50 DEG C；
(2) continue, at 50 DEG C, in the system after above-mentioned basification, to add (3- (2- chloroethyl) acrylamido)
(this concentration of aqueous solution is 65 to the aqueous solution of hydroxypropyltrimonium chloride (purchased from thyrite Chemical Co., Ltd. of Huantai County, as follows)
Weight %, it is 110g that consumption makes the addition of (3- (2- chloroethyl) acrylamido) hydroxypropyltrimonium chloride), and stir
Mixing 30min；At 80 DEG C, then carry out quaterisation 3.5h；
(3) product after above-mentioned quaterisation is cooled to room temperature, and ph to 7 is adjusted using hydrochloric acid；Then sucking filtration, uses
Isopropanol washing filter cake 3 times, and filter cake is placed in 90 DEG C of vacuum drying ovens 20h is dried, obtain the solid of 200g, this solid is
For modification of chitosan c3.
Through infrared, proton nmr spectra and the detection of carbon analysis of spectrum, there is in this modification of chitosan the structure list shown in formula (2)
First (wherein, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-ch2-), and content is 70 weight %；This changes
Property shitosan number-average molecular weight be 54000.
Embodiment 4
The present embodiment is used for modification of chitosan of the present invention and preparation method thereof is described.
According to the method for embodiment 1, except for the difference that, the number-average molecular weight of the shitosan adopting in step (1) is 16000,
Thus the modification of chitosan c4 finally obtaining.
Through infrared, proton nmr spectra and the detection of carbon analysis of spectrum, there is in this modification of chitosan the structure list shown in formula (2)
First (wherein, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-), and content is 50 weight %；This modified shell
The number-average molecular weight of polysaccharide is 28000.
Embodiment 5
The present embodiment is used for modification of chitosan of the present invention and preparation method thereof is described.
According to the method for embodiment 1, except for the difference that, the number-average molecular weight of the shitosan adopting in step (1) is 60000,
Thus the modification of chitosan c5 finally obtaining.
Through infrared, proton nmr spectra and the detection of carbon analysis of spectrum, there is in this modification of chitosan the structure list shown in formula (2)
First (wherein, r1-r3Selected from methyl, r4It is selected from-ch2-ch2-ch2-, r5It is selected from-ch2-), and content is 82 weight %；This modified shell
The number-average molecular weight of polysaccharide is 72000.
Test case 1
Respectively by the above modification of chitosan c1-c5 of 4 weight portions and potassium chloride, polyetheramine (purchased from Tianjin Heng Zhixin section
Skill Co., Ltd hx-amine) mix with the clear water of 100 weight portions, resulting solution is respectively defined as shale control agent test solution
Y1-y5 and dy1-dy2, and using clear water as blank.
Above-mentioned test solution is down to room temperature and respectively carry out rolling rate of recovery test before ageing and after 150 DEG C of aging 16h
With the test of shale expansion rate, the results are shown in Table shown in 1, wherein:
(1) test process of rolling rate of recovery includes: measures 350ml shale control agent test solution (inclusion clear water) respectively in height
Stir in cup, and pour into standby in aging tank after high-speed stirred 5min, take 2mm-3.8mm shale to dry to constant weight at 105 ± 3 DEG C fall
To room temperature.Weigh 10g shale (g0), put in test solution and roll 16h at 150 DEG C, take out after cooling, use aperture 0.42mm
Sieve reclaims core, dries to constant weight at 105 ± 3 DEG C, is down to room temperature and claims to reclaim core quality g1.Claimed overweight recovery core again
Put in the shale control agent test solution (inclusion clear water) of this test and roll 16h at 150 DEG C, take out after cooling, use aperture
0.42mm sieve reclaims core, dries to constant weight at 105 ± 3 DEG C, is down to room temperature and claims to reclaim core quality g2.
Shale recovery ratio a: r1=g1/g0× 100%；Secondary shale recovery ratio: r2=g2/g0× 100%
Wherein, g0For former shale quality, g；g1For the shale quality after secondary recovery, g；g2For the shale matter after secondary recovery
Amount, g；r1For a shale recovery ratio, %；r2For secondary shale recovery ratio, %.
(2) test process of shale expansion rate includes: measures 20ml shale control agent test solution standby in beaker；Weigh
The drilling fluid bentonite 5g dried at 105 DEG C, loads in test barrel, and stopper rod is inserted survey cylinder, keeps five points under 1mpa
Clock, is obtained experiment rock core, measures rock-sample initial height h0.The survey cylinder with rock core is arranged on shale expansion instrument, will be to be measured
Cylinder is surveyed in test solution injection, after soaking 24h, writes down rock core swell increment ht.
Shale expansion rate: e=(ht-h0)/h0× 100%.
Table 1
Be can be seen that compared with potassium chloride and conventional polyetheramine by the data of upper table 1, modification of chitosan has preferably
Shale inhibition energy, and still there is preferable effect it is seen that modification of chitosan has preferable temperature resistance in 150 DEG C of aging rear its
Property.
Embodiment 6
The present embodiment is used for the drilling fluid of the present invention is described.
1# drilling fluid: the water of 100 weight portions, the sodium bentonite of 4 weight portions is (purchased from the dimension bentonite technical research of Weifang China
Center, as follows), the polyacrylamide potassium salt of 0.5 weight portion (purchased from Renqiu City Hong Ze petrochemical industry company limited k-pam, with
Under identical), potassium humate (purchased from the sincere Science and Technology Ltd. in stone Dabo, Beijing trade mark khm) khm of 3 weight portions, the sulphur of 2 weight portions
Methyl phenolic resin (purchased from the smp-ii of Xin Lei oilfield additive company limited of Xinxiang City, as follows), the lubricant of 2 weight portions
(purchased from the modified phospholipid of the Shanghai You Chuan Industrial Co., Ltd. fhgt-g trade mark), the modification of chitosan c1 of 2 weight portions.
Test case 2
Drilling fluid key property is tested: by drilling fluid before ageing and after 120 DEG C of aging 16h, tests table at room temperature
See viscosity (av), plastic viscosity (pv), yield value (yp), gel initial, 10-minute gel strength, middle filter pressing vector (api), High Temperature High Pressure leak-off
Amount (hthl), density and ph, result is as shown in table 2, wherein:
Plastic viscosity (pv) is using the fast viscometer of normal form six side according to specified in national standard gb/t29170-2012
Method measures, and unit is mpa s, pv=θ600-θ300.
Apparent viscosity (av) is using the fast viscometer of normal form six side according to specified in national standard gb/t29170-2012
Method measures, and unit is mpa s,
Yield value (yp) is using the fast viscometer method according to specified in national standard gb/t29170-2012 of normal form six
Measure, yp=0.5 (2 θ300-θ600), unit is pa.
Ratio of dynamic shear force/yield value to plastic viscosity:It is successively read φ 600 and φ 300 using six fast rotating cylinder viscometers.
Gel initial and 10-minute gel strength be using the fast viscometer of normal form six according to specified in national standard gb/t29170-2012
Method measures:Unit pa.
Api refers to middle filter pressing vector, is to commit a breach of etiquette using middle filter pressing to be surveyed according to the method in sy/t 5621-93 standard
Amount, unit is ml.
Hthp refers to high temperature and high pre ssure filtration, is according to national standard gb/t29170-2012 using high pressure high temperature filter tester
Specified in method measure, unit is ml.
Table 2
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (18)
1. a kind of modification of chitosan is it is characterised in that described modification of chitosan has a modified group shown in following formula (1):
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
2. modification of chitosan according to claim 1, wherein, described modification of chitosan has the structure shown in following formula (2)
Unit:
Formula (2)
3. modification of chitosan according to claim 2, wherein, on the basis of described modification of chitosan gross weight, described formula
(2) content of the construction unit shown in is more than 40 weight %, preferably 50-90 weight %, more preferably 60-85 weight %,
It is still more preferably 65-80 weight %.
4. the modification of chitosan according to any one in claim 1-3, wherein, r1-r3It is each independently selected from c1-c6
Alkyl, r4And r5It is each independently selected from the alkylidene of c1-c6；
Preferably, r1-r3It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl, r4And r5Independently of one another
It is selected from-ch2-、-ch2-ch2-、-ch2-ch2-ch2-、-ch(ch3)-ch2-、-ch2-ch(ch3)-and-ch2-(ch2)2-ch2-.
5. the modification of chitosan according to any one in claim 1-4, wherein, the equal molecule of number of described modification of chitosan
Measure as 20000-80000, preferably 40000-70000, more preferably 50000-60000.
6. a kind of preparation method of modification of chitosan is it is characterised in that the method includes:
(1) in the presence of alkali compoundss, in a solvent, shitosan is carried out basification；
(2) product after described basification is carried out quaterisation with the ammonium salt providing the modified group shown in following formula (1),
Formula (1)
Wherein, r1-r3It is each independently selected from the alkyl of c1-c8, r4And r5It is each independently selected from the alkylidene of c1-c8.
7. method according to claim 6, wherein, the modification of chitosan of the method gained has the modification shown in formula (1)
Group；
Preferably, described modification of chitosan has a construction unit shown in following formula (2):
Formula (2)
Preferably, r1-r3It is each independently selected from the alkyl of c1-c6, r4And r5It is each independently selected from the alkylidene of c1-c6；More
Preferably, r1-r3It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl, r4And r5Select independently of one another
From-ch2-、-ch2-ch2-、-ch2-ch2-ch2-、-ch(ch3)-ch2-、-ch2-ch(ch3)-and-ch2-(ch2)2-ch2-.
8. the method according to claim 6 or 7, wherein, in step (1), described alkali compoundss are sodium hydroxide, hydrogen-oxygen
Change one or more of potassium and Lithium hydrate；
Preferably, with respect to the shitosan of 100 weight portions, the consumption of described alkali compoundss is 2-8 weight portion.
9. the method according to claim 6 or 7, wherein, in step (1), described solvent be isopropanol, methanol, ethanol and
One or more of propanol；
Preferably, with respect to the shitosan of 100 weight portions, the consumption of described solvent is 800-2000 weight portion, preferably 900-
1500 weight portions.
10. method according to claim 6, wherein, in step (2), described ammonium salt is (3- (2- chloromethyl) acrylamide
Base) hydroxypropyltrimonium chloride, (3- (2- chloromethyl) acrylamido) propyl group triethyl ammonium chloride, (3- (2- chloroethyl) third
Alkene acylamino-) hydroxypropyltrimonium chloride, (3- (2- chloroethyl) acrylamido) propyl group triethyl ammonium chloride, (4- (2- chloromethane
Base) acrylamido) in butyl trimethyl ammonium chloride and (4- (2- chloromethyl) acrylamido) butyl triethyl ammonium chloride
One or more；
Preferably, with respect to the shitosan of 100 weight portions, the consumption of described ammonium salt is 40-200 weight portion, preferably 80-150
Weight portion, more preferably 100-120 weight portion.
11. methods according to any one in claim 6-10, wherein, in step (1), the number of described shitosan is divided equally
Son is measured as 1500-8000, preferably 2000-6000, more preferably 3000-4000.
12. methods according to any one in claim 6-11, wherein, in step (1), the condition of described basification
Including: temperature is 40-70 DEG C, and the time is 2-8h；
Preferably, in step (2), the condition of described quaterisation includes: temperature is 65-90 DEG C, and the time is 2-6h.
The modification of chitosan that 13. methods described in any one in claim 6-12 are obtained.
In 14. claim 1-5 and 13 modification of chitosan described in any one as the shale control agent in drilling fluid in oil
Application in pneumatic drill well.
15. is a kind of water base as shale control agent containing the modification of chitosan described in any one in claim 1-5 and 13
Drilling fluid.
16. water-base drilling fluids according to claim 15, wherein, with respect in the described water-base drilling fluid of 100 weight portions
Water, the consumption of described modification of chitosan is 1-3 weight portion.
Application in oil/gas drilling for the water-base drilling fluid described in 17. claim 15 or 16.
18. applications according to claim 17, wherein, described oil/gas drilling is shale gas drilling well.
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| CN116285915A (en) * | 2022-09-08 | 2023-06-23 | 中石化石油工程技术服务有限公司 | Environment-friendly high-temperature-resistant drilling fluid for shale deep well and preparation method thereof |
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