CN106336467B - Modification of chitosan and preparation method thereof and application and drilling fluid and its application as shale control agent - Google Patents
Modification of chitosan and preparation method thereof and application and drilling fluid and its application as shale control agent Download PDFInfo
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- CN106336467B CN106336467B CN201610726240.9A CN201610726240A CN106336467B CN 106336467 B CN106336467 B CN 106336467B CN 201610726240 A CN201610726240 A CN 201610726240A CN 106336467 B CN106336467 B CN 106336467B
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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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- 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
Abstract
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 and drilling fluid and its application as shale control agent.The modification of chitosan has the modified group shown in following formula (1).The present invention is applied to above-mentioned modification of chitosan as shale control agent in oil/gas drilling, particularly in shale gas drilling well, excellent inhibition can be obtained, and the modification of chitosan has good heat resistance, higher inhibitory action can be kept at a higher temperature for a long time, and the modification of chitosan has the biodegradable of chitosan, belong to environmentally friendly shale control agent.
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 and drilling fluid and its application as shale control agent.
Background technology
With the raising of human living standard, consumption of the mankind to the energy is growing.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 of change, the exploitation upsurge of the very big unconventional energy resource for having driven the whole world.In the recent period, domestic also great attention shale gas etc. is non-
The exploitation of conventional energy resource.Oil base drilling fluid and 30% water-based drilling fluid are applied in the exploitation about 70% of current external shale gas,
Then domestic almost all application oil base drilling fluid.Heavy environmental pollution be present in the application of oil base drilling fluid.Environmental problem
The attention of various countries is caused, application of the oil base drilling fluid in future is possible to face disabled danger, therefore water-based drilling
Liquid is the developing direction of following drilling fluid.
Shale is a kind of sedimentary rock, matter hardness is crisp, permeability is low, the development of nano-micron pore gap is abundant.Shale gas is largely enriched with
In shale.In drilling process, on the one hand because hydration swelling, scattered migration, corrosion point occur for the clay mineral of oil-gas Layer
Dissipate, so as to cause the injury of unrepairable to reservoir；On the other hand, drilling fluid, which enters oil-gas Layer, will cause water lock, emulsification, wetting
Reversion and chemical precipitation.For the accumulation feature of shale, traditional mining type can not meet the exploitation of shale gas.Shale gas
Exploitation is based on shallow-layer extended reach well, cluster horizontal well well spacing.Because the nano-micron pore gap development of shale is abundant, in long horizontal sections
Drilling process, it is easy to cause leakage, caves in, the drilling problem such as undergauge, bit freezing, Wellbore Stability, which turns into, restricts water-base drilling fluid
The bottleneck of development.
For water-base drilling fluid, ensure that the wellbore stability key of shale is to improve drilling fluid rejection ability.Wherein,
Inhibitor is a kind of additive of the rejection ability of preferred raising water-base drilling fluid.At present, inhibitor has many industrial products,
Most of shale control agent used both at home and abroad is polyamine class shale control agent, and it has, and inhibition is good, less toxic, compatibility
It is good, but its temperature resistant capability is poor；And the shale inhibition of other shale control agents with temperature resistant capability is poor, during suppression
Between it is shorter, and be mostly the polymer that is not easily decomposed.
The content of the invention
It is an object of the invention to overcome existing shale control agent to be difficult to have good inhibition and heat resistance concurrently
The defects of, there is provided a kind of modification of chitosan having good inhibition and heat resistance concurrently and environmentally friendly and preparation method thereof and
Application and drilling fluid and its application as shale control agent.
To achieve these goals, the present invention provides a kind of modification of chitosan, and the modification of chitosan has following formula (1) institute
The modified group shown：
Formula (1)
Wherein, R1-R3It is each independently selected from C1-C8 alkyl, R4And R5It is each independently selected from C1-C8 alkylidene.
Present invention also offers a kind of preparation method of modification of chitosan, this method includes：
(1) in the presence of alkali compounds, in a solvent, chitosan is subjected to basification；
(2) it is ammonium salt progress of the product after the basification with providing the modified group shown in following formula (1) is quaternized
Reaction,
Formula (1)
Wherein, R1-R3It is each independently selected from C1-C8 alkyl, R4And R5It is each independently selected from C1-C8 alkylidene.
Present invention also offers the modification of chitosan as made from the above method.
Present invention also offers by above-mentioned modification of chitosan as the shale control agent in drilling fluid in oil/gas drilling
Using.
Present invention also offers a kind of water-base drilling fluid for containing above-mentioned modification of chitosan as shale control agent.
Present invention also offers application of the above-mentioned water-base drilling fluid in oil/gas drilling.
The present invention is applied to above-mentioned modification of chitosan as shale control agent in oil/gas drilling, particularly shale gas drilling well
In, excellent inhibition can be obtained, and the modification of chitosan has good heat resistance, can be for a long time higher
At a temperature of keep higher inhibitory action, and the modification of chitosan has the biodegradable of chitosan, belongs to environment
The shale control agent of friendly.Therefore, can be in high temperature page as shale control agent by using the modification of chitosan of the present invention
Scattered, expansion migration of aquation of shale etc. can be suppressed in rock drilling process well, and environment will not be polluted.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
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 clay easy aquation, expansion, scattered, migration characteristic in itself, often result in the borehole well instability in drilling process, collapse
The problems such as collapsing, and shale control agent is exactly to prevent shale and clay mineral hydration swelling with ion exchange by Electrostatic Absorption, is prevented
The only chemical reagent of cave-in.
The present invention provides a kind of modification of chitosan, and the modification of chitosan has the modified group shown in following formula (1)：
Formula (1)
Wherein, R1-R3It is each independently selected from C1-C8 alkyl, R4And R5It is each independently selected from C1-C8 alkylidene.
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, Electrostatic Absorption and ion exchange are passed through
The hydration swelling of clay mineral and scattered migration are prevented, so as to prevent the generation of borehole well instability and problem of caving in.Especially for
For shale gas drilling well, modification of chitosan of the invention is particularly well suited as the shale control agent of shale gas drilling well, in page
During rock pneumatic drill well, modification of chitosan main chain of the invention has adsorption group, and side chain has more cation groups,
So, modification of chitosan in aqueous on the one hand due to its protonation after react positively charged so as to adsorb in shale surface, according to
Adsorbed by force in shale surface by electrostatic interaction, weaken the electrostatic repulsion and surface hydration film repulsion of shale surface；On the other hand, change
Property chitosan on substantial amounts of adsorption group, can be in shale surface multiple spot absorption simultaneously, so as to which shale is tightly strapped in into one
Rise, prevent its hydration swelling.In addition, the anion of the cation group and shale surface on modification of chitosan is made by electrostatic
With also further preventing the hydration swelling of shale：
Formula (2)
That is, it is preferable that the 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 be to be able to more preferable
Inhibition and heat resistance when ground plays above-mentioned modification of chitosan as shale control agent, it is preferable that with the modification
On the basis of chitosan gross weight, the content of the construction unit shown in the formula (2) is more than 40 weight %, and preferably 50-90 is heavy
%, more preferably 60-85 weight % are measured, is still more preferably 65-80 weight %.
In the present invention, above-mentioned C1-C8 alkyl for example can be methyl, it is ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl etc..
Above-mentioned C1-C8 alkylidene can be the alkylidene that above-mentioned C1-C8 alkyl is formed.
Under preferable case, R1-R3It is each independently selected from C1-C6 alkyl, 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-propyl, 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, R4Selected from-CH2-CH2-CH2-, R5Selected from-
CH2-。
In another preferred embodiment of the present invention, R1-R3Selected from ethyl, R4Selected from-CH2-CH2-CH2-, R5Choosing
From-CH2-。
In another preferred embodiment of the present invention, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Choosing
From-CH2-CH2-。
In another preferred embodiment of the present invention, R1-R3Selected from ethyl, R4Selected from-CH2-CH2-CH2-, R5Choosing
From-CH2-CH2-。
In the preferred embodiment of the present invention, R1-R3Selected from methyl, R4Selected from-CH2-(CH2)2-CH2-, R5Choosing
From-CH2-。
In another preferred embodiment of the present invention, R1-R3Selected from ethyl, R4Selected 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
Compatibility suitable for water-base drilling fluid considers that under preferable case, the number-average molecular weight of the modification of chitosan is 20000-80000,
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, so as to carry certain anion.Therefore, there is no particular limitation to the anion by the present invention, can be conventional ammonium
Anion in salt, such as Cl can be selected from-、Br-、I-One or more in.
Present invention also offers a kind of preparation method of modification of chitosan, this method includes：
(1) in the presence of alkali compounds, in a solvent, chitosan is subjected to basification；
(2) it is ammonium salt progress of the product after the basification with providing the modified group shown in following formula (1) is quaternized
Reaction,
Formula (1)
Wherein, R1-R3It is each independently selected from C1-C8 alkyl, R4And R5It is each independently selected from C1-C8 alkylidene.
According to the present invention, although as long as the present invention can be obtained by carrying out preparation according to the preparation method of above-mentioned modification of chitosan
It is required can be as the product of shale control agent, especially modification of chitosan described above will be made in the above method,
Modification of chitosan i.e. obtained by this method has the modified group shown in formula (1).As described above, it is preferable that it is described
Modification of chitosan has the construction unit shown in following formula (2).Also, the specific descriptions of each group therein are also such as above institute
Description, it will not be repeated here.
In the preparation method of above-mentioned modification of chitosan, in step (1), chitosan is subjected to basification, enables to shell
Glycan is easier to dissociate ammonium root group, so as to carry out the quaterisation in step (2).Wherein, the alkalescence
Compound can use the conventional compound that basification can be carried out to chitosan Ji in this area, such as sodium methoxide, methanol
One or more in potassium, caustic alcohol, potassium ethoxide, sodium tert-butoxide, sodium hydroxide, potassium hydroxide and lithium hydroxide etc., it is preferably
One or more in sodium hydroxide, potassium hydroxide and lithium hydroxide, particularly preferably sodium hydroxide.In order to be suitable to
The chitosan of the quaterisation, it is preferable that relative to the chitosan of 100 parts by weight, the alkali compounds is (with dry weight
Meter) dosage be 2-8 parts by weight, preferably 3-5 parts by weight.Above-mentioned alkali compounds can introduce in solid form, can also
Introduce as a solution, it is preferred to use the form of solution, for example with the form for the aqueous solution that concentration is 50-70 weight %.
According to the present invention, wherein the selection of the chitosan can be selected according to required modification of chitosan, such as
It is that 20000-80000 (is preferably 40000-70000, is still more preferably 50000- needing to prepare number-average molecular weight
60000) during modification of chitosan, the number-average molecular weight of preferably described chitosan is 15000-80000, more preferably 20000-
60000, it is still more preferably 30000-40000.
According to the present invention, the basification will be carried out in a solvent, to cause chitosan to be at preferable dissolved form
State and the contact between alkali compounds is also more abundant.Preferably, the solvent is isopropanol, methanol, ethanol and propyl alcohol
In one or more, the dissolving of chitosan can be advantageous to using such solvent, the quaterisation after being also suitable for
Carry out.Under preferable case, relative to the chitosan of 100 parts by weight, the dosage of the solvent is 800-2000 parts by weight, is preferably
900-1500 parts by weight.
According to the present invention, in order to substantially more reach the purpose of alkalization chitosan, above-mentioned steps (1) preferably first will
Chitosan mixes with solvent, preferably to form the solution of chitosan, is re-introduced into alkali compounds and carries out basification.It is preferred that feelings
Under condition, the condition of the basification includes：Temperature is 40-70 DEG C (being preferably 45-60 DEG C), and the time is that 2-8h (is preferably 3-
5h)。
According to the present invention, in step (2), by above-mentioned alkalinization, on the one hand also system is caused to maintain certain alkali
Property environment, in this case, introduce and the ammonium salt of the modified group is provided carries out quaterisation, you can so that chitosan
The modified group shown in above formula (1) is connected, so as to obtain the modification of chitosan containing the construction unit shown in formula (2).
Wherein, there is provided the ammonium salt of the modified group can be according to above selecting the specific descriptions of modified group
Select, it is preferable that the ammonium salt is the compound shown in formula (3)：
Formula (3)Wherein, X for example can be
Cl, Br, I etc., L-Anion can be the various anion entrained by ammonium salt, such as can be Cl-、Br-、I-Deng.
In a kind of preferred embodiment of the present invention, in step (2), the ammonium salt is (3- (2- chloromethyls) propylene
Acylamino-) hydroxypropyltrimonium chloride (namely in compound shown in formula (3), R1-R3Selected from methyl, R4Selected from-CH2-CH2-
CH2-, R5Selected from-CH2-, X Cl, L-For Cl-), (3- (2- chloromethyls) acrylamido) propyl group triethyl ammonium chloride (namely formula
(3) in compound shown in, R1-R3Selected from ethyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-, X Cl, L-For Cl-)、(3-
(2- chloroethyls) acrylamido) hydroxypropyltrimonium chloride (namely in compound shown in formula (3), R1-R3Selected from methyl, R4Choosing
From-CH2-CH2-CH2-, R5Selected from-CH2-CH2-, X Cl, L-For Cl-), the second of (3- (2- chloroethyls) acrylamido) propyl group three
Ammonium chloride (namely in compound shown in formula (3), R1-R3Selected from ethyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-
CH2-, X Cl, L-For Cl-), (4- (2- chloromethyls) acrylamido) butyl trimethyl ammonium chloride (namely chemical combination shown in formula (3)
In thing, R1-R3Selected from methyl, R4Selected from-CH2-(CH2)2-CH2-, R5Selected from-CH2-, X Cl, L-For Cl-) and (4- (2- chloromethanes
Base) acrylamido) butyl triethyl ammonium chloride (namely in compound shown in formula (3), R1-R3Selected from ethyl, R4Selected from-CH2-
(CH2)2-CH2-, R5Selected from-CH2-, X Cl, L-For Cl-) in one or more.
In order to connect upper appropriate modified group on chitosan, it is more than 40 weight % particularly to obtain content
Shown in the formula (2) of (being preferably 50-90 weight %, more preferably 60-85 weight %, be still more preferably 65-80 weight %)
Construction unit, it is preferable that in step (2), relative to the chitosan of 100 parts by weight, the dosage of the ammonium salt is 40-200 weights
Measure part, preferably 80-150 parts by weight, more preferably 100-120 parts by weight.Wherein, the ammonium salt can carry in solid form
For that can also provide as a solution, it is preferable that the ammonium salt carries in the form of concentration is the 60-70 weight % aqueous solution
For.
It is excellent in order to cause the quaterisation more successfully to carry out in above-mentioned steps (2) according to the present invention
Choosing first by the product after the basification and after providing the ammonium salt of the modified group and mix, progress it is described it is quaternized instead
Should.Wherein, the condition of the mixing preferably includes：Temperature is 40-70 DEG C (be preferably 45-60 DEG C), the time be 10-40min (preferably
For 20-30min).Preferably, the condition of the quaterisation includes：Temperature is 65-90 DEG C (be preferably 70-80 DEG C), the time
For 2-6h (being preferably 3.5-5h).
According to the present invention, in order to which the modification of chitosan of gained is extracted, the preparation side of above-mentioned modification of chitosan
Method can also include, and the product after quaterisation is neutralized, separation of solid and liquid (being carried out for example with the mode of suction filtration), washed
Wash solid phase (being washed using above-mentioned solvent, washing times can be 2-5 times) and dry.Wherein, neutralize and cause the anti-of gained
The pH of system is answered between 6.5-7.5, particularly in 7-7.5 or so.Such as it can be neutralized using hydrochloric acid.Wherein, dry
Condition can for example include：Temperature is 80-100 DEG C, time 20-48h.
Present invention also offers the modification of chitosan as made from the above method.As long as the modification of chitosan passes through the above method
It is the present invention required modification of chitosan here to be made, but description specifically still may refer to above to modified shell
The description of glycan.
Present invention also offers by above-mentioned modification of chitosan as the shale control agent in drilling fluid in oil/gas drilling
Using.According to the present invention, the modification of chitosan is used in water-base drilling fluid as shale control agent, 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 water-base drilling fluid for containing above-mentioned modification of chitosan as shale control agent.As above institute
Description, according to the present invention, the modification of chitosan is used in water-base drilling fluid as shale control agent, by the water base of gained
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 of rock is scattered, expansion is migrated etc., and environment will not be polluted.Preferably, the oil/gas drilling is shale pneumatic drill
Well, as described above, there is the drilling fluid of the modification of chitosan especially suitable for shale gas drilling well.
According to the present invention, the dosage of the modification of chitosan can select the conventional of shale control agent in water-base drilling fluid
Dosage, it is preferable that relative to the water in the water-base drilling fluid of 100 parts by weight, the dosage of the modification of chitosan is 1-3 weights
Measure part.
According to the present invention, there is no particular limitation to the water base drilling fluid system containing modification of chitosan by the present invention, can be with
For the conventional various water base drilling fluid systems in this area, as long as being added into the present invention into these conventional water base drilling fluid systems
Modification of chitosan.For example can be potassium chloride-polyglycol drilling fluid, organosilicon as such conventional drilling liquid system
One or more in drilling fluid and cationic drilling fluid.Potassium chloride-the polyglycol drilling fluid can be people in the art
Various potassium chloride-polyglycol drilling fluids known to member, such as 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 in ethylene glycol drilling fluid；The silicone drilling fluid can be well known to those skilled in the art each
Kind of silicone drilling fluid, the organosilicon in the silicone drilling fluid can be selected from methyl silicon sodium alcoholate, methyl silanol potassium and have
One or more in machine silicon humic acid potassium.The various sun that the cationic drilling fluid can be well known to those skilled in the art
Ion drilling fluid, the cation in the cationic drilling fluid can be chloro- selected from 2,3- epoxypropyltrimethylchloride chlorides, 3-
One or more in 2- hydroxypropyl-trimethyl ammonium chlorides and PAMC.
Normally, other additives as water-base drilling fluid, preferable case can also be contained in the water-base drilling fluid
Under, drilling fluid of the invention contains one kind or more in bentonite, tackifier, anti-sloughing agent, fluid loss additive, lubricant and heavy weight additive
Kind.
Wherein, the bentonite refers to the clay using montmorillonite as main mineral constituent, and it has imparting drilling fluid is viscous to cut
The effect of power and leak-off wave making machine, such as can be sodium bentonite and/or calcium-base bentonite, preferably sodium bentonite.More
Preferably, relative to the water in the water-base drilling fluid of 100 parts by weight, the bentonitic content is 2-6 parts by weight, more excellent
Elect 3-5 parts by weight as.
Wherein, the tackifier can improve the viscous shear force of drilling fluid, such as can be polyacrylamide sylvite (KPAM), poly-
One kind in anionic cellulose (such as PAC141) and the copolymer of acrylamide and PAA (such as the trade mark is 80A51)
Or a variety of, preferably polyacrylamide sylvite.It is highly preferred that relative to the water in the water-base drilling fluid of 100 parts by weight, institute
The content for stating tackifier is 0.3-1 parts by weight, more preferably 0.4-0.8 parts by weight.
Wherein, the anti-sloughing agent can aid in bionical shale control agent to prevent hole collapse, improve borehole wall stability, example
Such as can be one in potassium humate (KHM), organosilicon (such as the trade mark is GF-1) and sulfonated gilsonite (such as the trade mark is FT-1A)
Kind is a variety of, preferably potassium humate.It is highly preferred that relative to the water in the water-base drilling fluid of 100 parts by weight, it is described anti-
The content of agent of collapsing is 1-3 parts by weight.
Wherein, the fluid loss additive can improve wellbore liquid leaching loss wave making machine, such as 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 is SPNH) and amphoteric ion polymer JT-888
One or more, preferably SMP-II and/or SPNH.It is highly preferred that relative in the water-base drilling fluid of 100 parts by weight
Water, the content of the fluid loss additive is 1-3 parts by weight, more preferably 1.5-2 parts by weight.
Wherein, the wetting agent can improve drilling fluid lubricating performance, prevent the underground such as bit freezing complicated state, such as can be with
For sulfonation oil foot (such as the trade mark is FK-10), diesel oil and surfactant mixture (such as trade mark is FRH) and fatty glyceride
With the one or more in surfactant mixture (such as trade mark is FK-1), modified phospholipid.It is highly preferred that relative to 100 weights
The water in the water-base drilling fluid of part is measured, the content of the lubricant is 0.5-2 parts by weight.
Wherein, the density for acting as adjusting drilling fluid of the heavy weight additive reaches required density, such as can be barite
(such as can be barite of the barium sulfate content more than 90 weight %), organic salt (weigh-1, weigh-2 (active component
For potassium formate), weigh-3, Organic Sodium Salt GD-WT) etc. in one or more.Relative to the drilling fluid of 100 parts by weight
In water, it is preferable that the content of the heavy weight additive is 200-400 parts by weight, more preferably 330-350 parts by weight.
The various materials that above-mentioned additive is can be commercially available product, can also be made according to the conventional method in this area, this
In repeat no more.
Present invention also offers application of the above-mentioned water-base drilling fluid in oil/gas drilling.
, can be in high temperature shale drilling well as shale control agent by using the modification of chitosan of the present invention according to the present invention
During can suppress scattered, expansion migration of aquation of shale etc. well, and environment will not be polluted.
The present invention will be described in detail by way of examples below.
In following preparation example and comparative example：
Number-average molecular weight is to use GPC gel chromatographies (laboratory apparatus is the gel permeation chrommatograph of waters companies of the U.S., model
For E2695) measure.
The content of construction unit shown in formula (2) refers to that the middle content of the construction unit shown in formula (2) accounts for whole modified shell
The percentage by weight of glycan.
Embodiment 1
The present embodiment is used to illustrate modification of chitosan of the present invention and preparation method thereof.
(1) by 100g chitosan (be purchased from thyrite Chemical Co., Ltd. of Huantai County, number-average molecular weight 35000, below
It is dissolved in 1300g isopropanol together), then adding sodium hydrate aqueous solution, (concentration of aqueous solution is 60 weight %, and dosage causes
The addition of sodium hydroxide is 4g), and the basification 4h at 60 DEG C；
(2) continue at 60 DEG C, (3- (2- chloromethyls) acrylamido) is added into the system after above-mentioned basification
(concentration of aqueous solution is 65 to the aqueous solution of hydroxypropyltrimonium chloride (being purchased from thyrite Chemical Co., Ltd. of Huantai County, as follows)
Weight %, dosage make it that the addition of (3- (2- chloromethyls) acrylamido) hydroxypropyltrimonium chloride is 100g), and stir
Mix 30min；Quaterisation 4h is then carried out at 80 DEG C；
(3) product after above-mentioned quaterisation is cooled to room temperature, and using salt acid for adjusting pH to 7；Then filter, use
Isopropanol washing filter cake 3 times, and filter cake is placed in 80 DEG C of vacuum drying chambers and dries 24h, 200g solid is obtained, the solid is
For modification of chitosan C1.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, there is the structure list shown in formula (2) in the modification of chitosan
Member (wherein, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-), and content is 80 weight %；The modification shell
The number-average molecular weight of glycan is 58000.
Embodiment 2
The present embodiment is used to illustrate modification of chitosan of the present invention and preparation method thereof.
(1) 100g chitosan is dissolved in 1000g propyl alcohol, then adding sodium hydrate aqueous solution, (aqueous solution is dense
Spend and make it that the addition of sodium hydroxide is 4g for 65 weight %, dosage), and the basification 3.5h at 55 DEG C；
(2) continue at 55 DEG C, (3- (2- chloromethyls) acrylamido) is added into the system after above-mentioned basification
(concentration of aqueous solution is 65 weight % to the aqueous solution of hydroxypropyltrimonium chloride, and dosage causes epoxypropyltrimethylchloride chloride
Addition be 100g), and be stirred 30min；Quaterisation 5h is then carried out at 75 DEG C；
(3) product after above-mentioned quaterisation is cooled to room temperature, and using salt acid for adjusting pH to 7；Then filter, use
Propanol rinse filter cake 3 times, and filter cake is placed in 90 DEG C of vacuum drying chambers and dries 24h, 200g solid is obtained, the solid is
Modification of chitosan C2.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, there is the structure list shown in formula (2) in the modification of chitosan
Member (wherein, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-), and content is 68 weight %；The modification shell
The number-average molecular weight of glycan is 50000.
Embodiment 3
The present embodiment is used to illustrate modification of chitosan of the present invention and preparation method thereof.
(1) 100g chitosan is dissolved in 950g isopropanol, then adding sodium hydrate aqueous solution, (aqueous solution is dense
Spend and make it that the addition of sodium hydroxide is 5g for 60 weight %, dosage), and the basification 5h at 50 DEG C；
(2) continue at 50 DEG C, (3- (2- chloroethyls) acrylamido) is added into the system after above-mentioned basification
(concentration of aqueous solution is 65 to the aqueous solution of hydroxypropyltrimonium chloride (being purchased from thyrite Chemical Co., Ltd. of Huantai County, as follows)
Weight %, dosage make it that the addition of (3- (2- chloroethyls) acrylamido) hydroxypropyltrimonium chloride is 110g), and stir
Mix 30min；Quaterisation 3.5h is then carried out at 80 DEG C；
(3) product after above-mentioned quaterisation is cooled to room temperature, and using salt acid for adjusting pH to 7；Then filter, use
Isopropanol washing filter cake 3 times, and filter cake is placed in 90 DEG C of vacuum drying chambers and dries 20h, 200g solid is obtained, the solid is
For modification of chitosan C3.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, there is the structure list shown in formula (2) in the modification of chitosan
Member (wherein, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-CH2-), and content is 70 weight %；This changes
Property chitosan number-average molecular weight be 54000.
Embodiment 4
The present embodiment is used to illustrate modification of chitosan of the present invention and preparation method thereof.
According to the method for embodiment 1, unlike, the number-average molecular weight of the chitosan used in step (1) for 16000,
So as to the modification of chitosan C4 finally obtained.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, there is the structure list shown in formula (2) in the modification of chitosan
Member (wherein, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-), and content is 50 weight %；The modification shell
The number-average molecular weight of glycan is 28000.
Embodiment 5
The present embodiment is used to illustrate modification of chitosan of the present invention and preparation method thereof.
According to the method for embodiment 1, unlike, the number-average molecular weight of the chitosan used in step (1) for 60000,
So as to the modification of chitosan C5 finally obtained.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, there is the structure list shown in formula (2) in the modification of chitosan
Member (wherein, R1-R3Selected from methyl, R4Selected from-CH2-CH2-CH2-, R5Selected from-CH2-), and content is 82 weight %；The modification shell
The number-average molecular weight of glycan is 72000.
Test case 1
The above modification of chitosan C1-C5 and potassium chloride of 4 parts by weight, polyetheramine (are purchased from Tianjin Heng Zhixin sections respectively
Skill Co., Ltd HX-AMINE) mixed with the clear water of 100 parts by weight, 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 before ageing and after 150 DEG C of aging 16h and carries out rolling rate of recovery test respectively
Test, the results are shown in Table shown in 1 with shale expansion rate, wherein：
(1) test process of rolling rate of recovery includes：350mL shale control agents test solution (including clear water) is measured respectively in height
Stir in cup, and pour into standby in aging tank after high-speed stirred 5min, take 2mm-3.8mm shale to be dried to constant weight at 105 ± 3 DEG C drop
To room temperature.Weigh 10g shale (G0), it is put into test solution at 150 DEG C and rolls 16h, taken out after cooling, with aperture 0.42mm
Sieve recovery core, dries to constant weight at 105 ± 3 DEG C, is down to room temperature and claims to reclaim core quality G1.Overweight recovery core will have been claimed again
It is put into the shale control agent test solution (including clear water) of the test and 16h is rolled at 150 DEG C, is taken out after cooling, use aperture
0.42mm sieve recovery cores, dry to constant weight at 105 ± 3 DEG C, are down to room temperature and claim to reclaim core quality G2。
Shale recovery ratio：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：It is standby in beaker to measure 20mL shale control agent test solutions；Weigh
The drilling fluid dried at 105 DEG C bentonite 5g, is fitted into test barrel, and stopper rod is inserted and surveys cylinder, and five points are kept under 1MPa
Clock, experiment rock core, measure rock-sample initial height h is made0.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
It is can be seen that by the data of upper table 1 compared with potassium chloride and conventional polyetheramine, modification of chitosan has preferable
Shale inhibition energy, and it still has preferable effect after 150 DEG C of agings, it is seen that modification of chitosan has preferable temperature resistance
Property.
Embodiment 6
The present embodiment is used for the drilling fluid for illustrating the present invention.
1# drilling fluids：The water of 100 parts by weight, the sodium bentonite of 4 parts by weight is (purchased from the dimension bentonite technical research of Weifang China
It is center, as follows), the polyacrylamide sylvite of 0.5 parts by weight (Renqiu City Hong Ze petrochemical industries Co., Ltd K-PAM is purchased from, with
Under it is identical), potassium humate (being purchased from the sincere Science and Technology Ltd. trade mark KHM in stone Dabo, Beijing) KHM of 3 parts by weight, the sulphur of 2 parts by weight
Methyl phenolic resin (is purchased from the SMP-II of Xin Lei oilfield additives Co., Ltd of Xinxiang City, as follows), the lubricant of 2 parts by weight
(modified phospholipid for being purchased from the Shanghai You Chuan Industrial Co., Ltd.s FHGT-G trades mark), the modification of chitosan C1 of 2 parts by weight.
Test case 2
Drilling fluid basic performance is tested：By drilling fluid before ageing and after 120 DEG C of aging 16h, table is tested at room temperature
See viscosity (AV), plastic viscosity (PV), yield value (YP), gel initial, 10-minute gel strength, middle filter pressing loss (API), HTHP leak-off
(HTHL), density and pH are measured, as a result as shown in table 2, wherein：
Plastic viscosity (PV) is to use six fast viscosimeter of normal form side according to specified in standard GB/T/T29170-2012
What method measured, unit mPas, PV=θ600-θ300。
Apparent viscosity (AV) is to use six fast viscosimeter of normal form side according to specified in standard GB/T/T29170-2012
What method measured, unit mPas,
Yield value (YP) is to use six fast viscosimeter of normal form method according to specified in standard GB/T/T29170-2012
Measure, YP=0.5 (2 θ300-θ600), unit Pa.
Ratio of dynamic shear force/yield value to plastic viscosity：φ 600 and φ 300 are successively read using six fast rotation viscometers.
Gel initial and 10-minute gel strength are to use six fast viscosimeter of normal form according to specified in standard GB/T/T29170-2012
What method measured：Unit Pa.
API refers to middle filter pressing loss, is that the method that press filtration is committed a breach of etiquette in SY/T 5621-93 standards in using is surveyed
Amount, unit mL.
HTHP refers to high temperature and high pre ssure filtration, is according to standard GB/T/T29170-2012 using high pressure high temperature filter tester
Specified in method measure, unit mL.
Table 2
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned 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 it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (32)
1. a kind of modification of chitosan, it is characterised in that the modification of chitosan has the modified group shown in following formula (1)：
Wherein, R1-R3It is each independently selected from methyl, ethyl, n-propyl, 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-。
2. modification of chitosan according to claim 1, wherein, the modification of chitosan has the structure shown in following formula (2)
Unit：
3. modification of chitosan according to claim 2, wherein, on the basis of the modification of chitosan gross weight, the formula
(2) content of the construction unit shown in is more than 40 weight %.
4. modification of chitosan according to claim 3, wherein, on the basis of the modification of chitosan gross weight, the formula
(2) content of the construction unit shown in is 50-90 weight %.
5. modification of chitosan according to claim 4, wherein, on the basis of the modification of chitosan gross weight, the formula
(2) content of the construction unit shown in is 60-85 weight %.
6. modification of chitosan according to claim 5, wherein, on the basis of the modification of chitosan gross weight, the formula
(2) content of the construction unit shown in is 65-80 weight %.
7. according to the modification of chitosan described in any one in claim 1-6, wherein, the equal molecule of number of the modification of chitosan
Measure as 20000-80000.
8. modification of chitosan according to claim 7, wherein, the number-average molecular weight of the modification of chitosan is 40000-
70000。
9. modification of chitosan according to claim 8, wherein, the number-average molecular weight of the modification of chitosan is 50000-
60000。
10. a kind of preparation method of modification of chitosan, it is characterised in that this method includes：
(1) in the presence of alkali compounds, in a solvent, chitosan is subjected to basification；
(2) product after the basification is subjected to quaterisation with providing the ammonium salt of the modified group shown in following formula (1),
Wherein, R1-R3It is each independently selected from methyl, ethyl, n-propyl, 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-。
11. according to the method for claim 10, wherein, the modification of chitosan obtained by this method has changing shown in formula (1)
Property group.
12. according to the method for claim 11, wherein, the modification of chitosan has the construction unit shown in following formula (2)：
13. according to the method described in any one in claim 10-12, wherein, in step (1), the alkali compounds is
One or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
14. the method according to claim 11, wherein, relative to the chitosan of 100 parts by weight, the alkali compounds
Dosage is 2-8 parts by weight.
15. according to the method described in any one in claim 10-12, wherein, in step (1), the solvent is methanol, second
One or more in alcohol and propyl alcohol.
16. according to the method for claim 15, wherein, relative to the chitosan of 100 parts by weight, the dosage of the solvent is
800-2000 parts by weight.
17. according to the method for claim 16, wherein, relative to the chitosan of 100 parts by weight, the dosage of the solvent is
900-1500 parts by weight.
18. according to the method for claim 10, wherein, in step (2), the ammonium salt is (3- (2- chloromethyls) acryloyl
Amino) hydroxypropyltrimonium chloride, (3- (2- chloromethyls) acrylamido) propyl group triethyl ammonium chloride, (3- (2- chloroethyls)
Acrylamido) hydroxypropyltrimonium chloride, (3- (2- chloroethyls) acrylamido) propyl group triethyl ammonium chloride, (4- (2- chlorine
Methyl) acrylamido) in butyl trimethyl ammonium chloride and (4- (2- chloromethyls) acrylamido) butyl triethyl ammonium chloride
One or more.
19. according to the method for claim 18, wherein, relative to the chitosan of 100 parts by weight, the dosage of the ammonium salt is
40-200 parts by weight.
20. according to the method for claim 19, wherein, relative to the chitosan of 100 parts by weight, the dosage of the ammonium salt is
80-150 parts by weight.
21. according to the method for claim 20, wherein, relative to the chitosan of 100 parts by weight, the dosage of the ammonium salt is
100-120 parts by weight.
22. according to the method described in any one in claim 10-12 and 16-21, wherein, in step (1), the chitosan
Number-average molecular weight be 1500-8000.
23. according to the method for claim 22, wherein, in step (1), the number-average molecular weight of the chitosan is 2000-
6000。
24. according to the method for claim 23, wherein, in step (1), the number-average molecular weight of the chitosan is 3000-
4000。
25. according to the method described in any one in claim 10-12,16-21 and 23-24, wherein, it is described in step (1)
The condition of basification includes：Temperature is 40-70 DEG C, time 2-8h；
In step (2), the condition of the quaterisation includes：Temperature is 65-90 DEG C, time 2-6h.
26. according to the method described in any one in claim 10-12, wherein, in step (1), the solvent is isopropanol.
27. the modification of chitosan as made from the method described in any one in claim 10-26.
28. the modification of chitosan in claim 1-9 and 27 described in any one is as the shale control agent in drilling fluid in oil
Application in pneumatic drill well.
29. a kind of modification of chitosan contained in claim 1-9 and 27 described in any one is as the water base of shale control agent
Drilling fluid.
30. water-base drilling fluid according to claim 29, wherein, relative in the water-base drilling fluid of 100 parts by weight
Water, the dosage of the modification of chitosan is 1-3 parts by weight.
31. application of the water-base drilling fluid described in claim 29 or 30 in oil/gas drilling.
32. application according to claim 31, wherein, the oil/gas drilling is shale gas drilling well.
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| CN107903335A (en) * | 2017-11-21 | 2018-04-13 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of heat-resistance type clay stabilization agent material |
| CN111574972B (en) * | 2020-06-19 | 2021-01-26 | 中国石油大学(华东) | Environment-friendly high-temperature-resistant shale inhibitor for water-based drilling fluid and preparation method thereof |
| CN113698510B (en) * | 2020-08-26 | 2022-06-17 | 中国石油大学(北京) | Environment-friendly bionic shale inhibitor taking modified chitosan as water-based drilling fluid |
| CN114316926B (en) * | 2022-01-11 | 2022-12-20 | 陕西科技大学 | Chitosan oil field clay stabilizer based on Mannich reaction and preparation method thereof |
| CN116285915B (en) * | 2022-09-08 | 2024-04-09 | 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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