CN106010482B - It is adapted to the environment-friendly type water base drilling fluid of shale gas horizontal well - Google Patents

It is adapted to the environment-friendly type water base drilling fluid of shale gas horizontal well Download PDF

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CN106010482B
CN106010482B CN201610340468.4A CN201610340468A CN106010482B CN 106010482 B CN106010482 B CN 106010482B CN 201610340468 A CN201610340468 A CN 201610340468A CN 106010482 B CN106010482 B CN 106010482B
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drilling fluid
formula
agent
bionical
particle
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CN106010482A (en
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蒋官澄
伍贤柱
马光长
张县民
贺垠博
刘凡
高德利
杨丽丽
屈刚
赵利
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China University of Petroleum Beijing
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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
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/06—Clay-free compositions
    • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/18—Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/34—Lubricant additives

Abstract

The present invention relates to petrochemical industry drilling applications, disclose a kind of environment-friendly type water base drilling fluid of suitable shale gas horizontal well, the drilling fluid contains a nanometer sealing agent, bionical solid wall agent, bionical shale control agent and filler, the nanometer sealing agent is modified nano SiO 2 particle, and its modified group includes modified acrylic acid copolymer chain；The bionical solid wall agent is that the carboxymethyl chitosan of the group from dopamine is grafted with main chain：The bionical shale control agent is made up of the construction unit of arginic construction unit and lysine；The filler be by weight ratio be 1：0.55‑6：The calcium carbonate composition of 0.55 6 1,600 2500 mesh, 1,050 1500 mesh and 500 1000 mesh.The drilling fluid of the present invention can obtain higher heat-resisting property, higher seal-off effect and inhibition and the feature of environmental protection, higher density can particularly be obtained, suitable for shale gas exploitation.

Description

It is adapted to the environment-friendly type water base drilling fluid of shale gas horizontal well
Technical field
The present invention relates to petrochemical industry drilling applications, in particular it relates to be adapted to the environmentally-friendly water-based brill of shale gas horizontal well Well liquid.
Background technology
With energy resource consumption the unconventional energy resource such as increasingly increase, shale gas, shale oil utilization gradually by weight Depending on.The explored shale oil gas pool reserve in China is huge, and exploration and development value is high.Exploitation shale gas mainly uses long section water at present Horizontal well, the method for multistage subsection pressure break, to improve well yield, lifting commercial mining value.Due to shale formation water sensitivity is strong, Fracture development, easily occur in drilling process collapsing, the complex situations such as undergauge, therefore the drill in fluid for exploiting shale gas faces Main difficult technical be long section horizontal well Wellbore Stability.
Current rammell horizontal well mainly uses oil base drilling fluid, can preferably solve Wellbore Stability.But shale Gas individual well quantum of output is generally relatively low, and the cost of oil-base mud is higher, reduces the industrial value of shale gas exploitation, and oil base drilling well The problems such as feature of environmental protection is poor, cost recovery is high, security difference be present in liquid.Water-base drilling fluid has that cost is relatively low, relatively more environmentally friendly, And the advantages that being easy to find oil and gas reservoir, but common water base drilling fluid system borehole wall stability is poor, lubricates anti-sticking scarce capacity, Limit application of the water-base drilling fluid in shale oil and gas development.
China's shale gas generally buries relatively deeply, such as Sichuan Basin Lower Cambrian Series shale gas-bearing formation buried depth 2000-3500 rice, ground Stressor layer is big, and the bad grounds such as super high pressure oil gas-bearing formation, brine layer and cream mud stone be present, and when boring, chance air content is larger and crack is sent out During the shale formation educated, gas overflowing amount, which increases severely, may result in the accidents such as blowout, well kick.Improving drilling fluid density can be effective Equilibrium strata pressure, borehole wall stability is improved, prevents complex situations.
At present, it is adapted to the water-base drilling fluid of shale gas exploitation perfect not enough, is mainly manifested in following aspects.
(1) high-temperature resistance has much room for improvement.With the increase of well depth and the rise of bottom hole temperature (BHT), water-base drilling fluid is resisted Warm nature requirement is also gradually being lifted.
(2) density is not generally high.The water-base drilling fluid of conventional density can not meet density of the high pressure formation to drilling fluid It is required that and improve the problem of drilling fluid density can bring such as rheological characteristic difference.
(3) inhibition is not high.Conventional water-base drilling fluid can not suppress the scattered of shale well, so as to cause well Wall unstability, while increase the problem of inhibition can bring such as rheological characteristic and seal-off effect difference again.
(4) seal-off effect is not high.The water-base drilling fluid of conventional density can not fully block the nano-micron pore gap in shale.
The content of the invention
It is an object of the invention to overcome, density existing for existing water-base drilling fluid is relatively low, temperature resistance is poor, seal-off effect With inhibition it is relatively low the defects of, there is provided one kind can obtain higher density, higher heat-resisting property, higher seal-off effect and inhibition Water-base drilling fluid.
To achieve these goals, the present invention provides a kind of water-base drilling fluid, and the drilling fluid contains a nanometer sealing agent, bionical Gu wall agent, bionical shale control agent and filler,
The nanometer sealing agent is modified nano SiO 2 particle, on the nano SiO 2 particle of the modification Modified group includes acrylic copolymer chain, and the construction unit in the acrylic copolymer chain following formula (1) Suo Shi by tying One or more offers in the monomer of structure shown in one or more and formula (2) in the monomer of structure；
Wherein, R1Selected from-OH, C1-C10 alkoxy or-N (R3)R2, R2And R3It is each independently selected from H, C1-C10 The alkyl of alkyl and the C1-C10 being substituted with a substituent, the substituent is-COOH ,-OH, halogen and-SO3One kind in H or It is a variety of；L is C0-C10 alkylidene；
The bionical solid wall agent is that the carboxymethyl chitosan of the group from dopamine is grafted with main chain, described from more Shown in the group such as formula (I-1) of bar amine：
The bionical shale control agent is made up of the construction unit shown in formula (3) and the construction unit shown in formula (4)：
The mol ratio of the construction unit shown in construction unit and formula (4) shown in formula (3) is 0.2-6：1, and it is described bionical The weight average molecular weight of shale control agent is 800-4000g/mol；
The filler be by weight ratio be 1：0.55-6：0.55-6 1600-2500 mesh, 1050-1500 mesh and 500- The calcium carbonate composition of 1000 mesh.
Water-base drilling fluid provided by the present invention can obtain higher heat-resisting property, higher seal-off effect and inhibition and environmental protection Property, higher density can also be particularly obtained, is a kind of suitable shale gas horizontal well especially suitable for shale gas horizontal wells Environment-friendly type water base drilling fluid.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the SEM figures of the nano SiO 2 particle of the modification of the gained of nanometer sealing agent preparation example 1.
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, the monomer of structure shown in formula (1) can be acrylamide monomers, and structure shown in formula (2) Monomer can also be acrylamide monomers, and in this case, the construction unit of the acrylic copolymer chain then can be with It is that the acrylamide monomers of the structure shown in the acrylamide monomers of structure and formula (2) as shown in formula (1) provide, such feelings Condition is also understood to the acrylic copolymer chain.
The present invention provides a kind of water-base drilling fluid, and the drilling fluid contains a nanometer sealing agent, bionical solid wall agent, the suppression of bionical shale Preparation and filler,
The nanometer sealing agent is modified nano SiO 2 particle, on the nano SiO 2 particle of the modification Modified group includes acrylic copolymer chain, and the construction unit in the acrylic copolymer chain following formula (1) Suo Shi by tying One or more offers in the monomer of structure shown in one or more and formula (2) in the monomer of structure；
Wherein, R1Selected from-OH, C1-C10 alkoxy or-N (R3)R2, R2And R3It is each independently selected from H, C1-C10 The alkyl of alkyl and the C1-C10 being substituted with a substituent, the substituent is-COOH ,-OH, halogen and-SO3One kind in H or It is a variety of；L is C0-C10 alkylidene；
The bionical solid wall agent is that the carboxymethyl chitosan of the group from dopamine is grafted with main chain, described from more Shown in the group such as formula (I-1) of bar amine：
The bionical shale control agent is made up of the construction unit shown in formula (3) and the construction unit shown in formula (4)：
The mol ratio of the construction unit shown in construction unit and formula (4) shown in formula (3) is 0.2-6：1, and it is described bionical The weight average molecular weight of shale control agent is 800-4000g/mol；
The filler be by weight ratio be 1：0.55-6：0.55-6 1600-2500 mesh, 1050-1500 mesh and 500- The calcium carbonate composition of 1000 mesh.
According to the present invention, although the nanometer sealing agent, the bionical solid wall agent and the bionical shale control agent can be with It is used cooperatively according to arbitrary proportion, and obtaining can promote drilling fluid to improve density, heat-resisting property, seal-off effect and inhibition, but It is, in order to enable the nanometer sealing agent, the bionical solid wall agent and the bionical shale control agent preferably to match somebody with somebody Close, under preferable case, the weight ratio of the nanometer sealing agent, the bionical solid wall agent and the bionical shale control agent is 100： 20-500：20-500, preferably 100：30-300：30-300, more preferably 100：50-200：50-200, for example, 100：50- 100：50-100.
According to the present invention, when the modified group on the nano SiO 2 particle of the modification includes acrylic copolymer After chain, equivalent on nano silicon grafting on the acrylic copolymer chain, so as to by hydrophobe group, The non-covalent bonds such as hydrogen bond form the suction-operated of space net structure and amide groups so that the silica nanometer of the modification Grain is not susceptible to reunite, will not agglomerate into the aggregate of bulky grain in other words when being used as sealing agent in for drilling fluid, protects Preferable dispersiveness is held, so that when for injecting in shale, gap of shale etc. can be preferably blocked, with the drilling fluid In other components, particularly ordinatedly reach raising ground with the bionical solid wall agent in the drilling fluid and bionical shale control agent Layer bearing capacity, stabilizing borehole, prevent leakage, the purpose of reservoir protec-tion.
In order to be better achieved above-mentioned purpose, under preferable case, R1Selected from-OH, C1-C6 alkoxy or-N (R3) R2, R2And R3The C1-C6 alkyl for being each independently selected from H, C1-C6 alkyl and being substituted with a substituent, the substituent for- COOH ,-OH and-SO3One or more in H；L is C1-C6 alkylidene.
It is highly preferred that R1Selected from-OH, C1-C4 alkoxy or-N (R3)R2, R2And R3It is each independently selected from H, C1-C4 Alkyl and the C1-C4 alkyl that is substituted with a substituent, the substituent is-COOH ,-OH and-SO3One or more in H； L is C1-C4 alkylidene.
It is further preferred that R1Selected from-OH, methoxyl group, ethyoxyl, propoxyl group or-N (R3)R2, R2And R3It is each independent Ground is selected from H, methyl, ethyl, propyl group, isopropyl, isobutyl group, the tert-butyl group, the methyl that is substituted with a substituent, is substituted with a substituent Ethyl, the propyl group being substituted with a substituent, the isopropyl being substituted with a substituent, the isobutyl group being substituted with a substituent and substituted base take The tert-butyl group in generation, the substituent in the alkyl of the substituted C1-C4 is-COOH and/or-SO3H；L is-CH2-、-CH2- CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2- or-CH2-CHCH3-CH2-.Herein In, the alkylidene that L is C0 refers to that the group of L both ends connection is directly connected to, it is understood that is that L is not present or is connecting key.
Wherein ,-N (R3)R2Instantiation for example can be：-NH-CH3、-NH-CH2-CH3、-NH-(CH2)2-CH3、- NH-(CH2)3-CH3、-NH-CH(CH3)-CH3、-NH-C(CH3)2-CH3、-NH-C(CH3)2-COOH、-NH-C(CH3)2-CH2- SO3H。
Wherein, the instantiation of C1-C10 alkyl for example can be：Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl Base, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl.
Wherein, the instantiation of C1-C10 alkoxy for example can be：Methoxyl group, ethyoxyl, propoxyl group, isopropyl oxygen Base, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, last of the ten Heavenly stems oxygen Base.
According to the present invention, the monomer of structure is preferably selected from one kind in the compound shown in following formula or more shown in formula (1) Kind：
In formula (1-1)：R1For-OH (also referred to as acrylic acid)；In formula (1-2)：R1For methoxyl group (also referred to as acrylic acid first Ester)；In formula (1-3)：R1For ethyoxyl (also referred to as ethyl acrylate)；In formula (1-4)：R1For propoxyl group (also referred to as acrylic acid third Ester)；In formula (1-5)：R1For-NH-CH3(also referred to as N methacrylamide)；In formula (1-6)：R1For-NH-CH2-CH3(also referred to as Make N- ethyl acrylamides)；In formula (1-7)：R1For-NH-C (CH3)2- COOH (also referred to as 2- acrylamides -2 Methylpropionic acid)； In formula (1-8)：R1For-NH-C (CH3)2-CH2-SO3H (also referred to as 2- acrylamide-2-methyl propane sulfonics).
According to the present invention, the monomer of structure is preferably selected from one kind in the compound shown in following formula or more shown in formula (2) Kind：
In formula (2-1)：L is-CH2- (also referred to as N, N '-methylene-bisacrylamide)；In formula (2-2)：L is-CH2-CH2- (also referred to as N, N '-ethylenebisacrylamide).
According to the present invention, in a kind of preferred embodiment of the present invention, the knot in the acrylic copolymer chain The structure list of structure shown in one or more and formula (2-a) in structure unit construction unit of structure as shown in following formula (1-a) One or more compositions in member：
Wherein, R1With L as hereinbefore defined.As can be seen that in the preferred embodiment, the acrylic compounds Copolymer chain be the construction unit of structure as shown in formula (1-a) in one or more and formula (2-a) shown in structure structure One or more linear copolymer chains formed in unit, can be random linear copolymer chains or block Linear copolymer chain or alternate linear copolymer chain, there is no particular limitation to this by the present invention.But for the sake of convenience, it is preferably Random linear copolymer chain.
The construction unit of structure shown in the construction unit of structure and formula (2-a) can basis respectively wherein shown in formula (1-a) The monomer of structure shown in the monomer of structure shown in formula (1) described above and formula (2) carries out preferred.
According to the present invention, although the structure list that the monomer of acrylic copolymer chain structure as shown in formula (1) provides The construction unit that the monomer of structure shown in member and formula (2) provides forms the modification base that can be used as on nano SiO 2 particle Group, with the surface of modified silica nanoparticle so that nano SiO 2 particle is used as nanometer sealing agent in drilling fluid When particle agglomeration can be avoided to play the plugging effect of modified silica nanoparticle into the phenomenon of larger particles, but be Enabling to the nano SiO 2 particle of the modification of gained, when as nanometer sealing agent can to play more preferable ion simultaneous Capacitive (mainly being observed by the fiting effect with other drilling fluid additives), high-temperature stability, salt-resistance, so as to preferably Coordinate the bionical solid wall agent in the drilling fluid and bionical shale control agent to reduce drilling fluid filtration, reach good closure effect Fruit, solve drilling shaft lining destabilization problems, under preferable case, in the acrylic copolymer chain, structure shown in the formula (1) The mol ratio for the construction unit that the monomer of structure shown in the construction unit and formula (2) that monomer provides provides is 1：0.5-5, more preferably For 1：1-2, it is still more preferably 1：1.3-1.6 most preferably 1：1.5-1.6.
According to the present invention, the molecular weight of the acrylic copolymer chain can change in relative broad range, as long as can The effect above is obtained, under preferable case, the weight average molecular weight of the acrylic copolymer chain is 100000-1500000g/ Mol, more preferably 120000-1400000g/mol, it is still more preferably 180000-1000000g/mol, more preferably 300000-1000000g/mol, more preferably 500000-900000g/mol, more preferably 600000-800000g/mol, example Such as it is 650000-760000g/mol.When the acrylic copolymer chain weight average molecular weight within the above range, particularly When in preferable scope, the nano SiO 2 particle of the modification of gained is enabled to obtain excellent property as nanometer sealing agent Energy.
According to the present invention, the content for the acrylic copolymer chain having on the nano SiO 2 particle of the modification can To be changed in relative broad range, as long as the nanometer sealing agent of function admirable can be obtained, under preferable case, with the modification Nano SiO 2 particle gross weight on the basis of, the content of the acrylic copolymer chain is more than 60 weight %, excellent Elect as more than 80 weight %, be still more preferably 90-98 weight %, most preferably 90-95 more preferably more than 90 weight % Weight %.
According to the present invention, the size of the nano SiO 2 particle of the modification can be entered according to the crack situation of rock stratum Row adjustment, but be evenly distributed according to the conventional cognitive of this area, general mud shale pore throat size between 10-30nm, due to , can be preferably scattered in drilling fluid when the nano SiO 2 particle of the modification of the present invention is as sealing agent, it will not be formed Big agglomerated particle, therefore, the nano SiO 2 particle of modification of the invention can have the particle diameter of relative broad range, and this is wider Also preferable plugging effect can be reached under scope particle diameter.So it is directed to the situation, it is preferable that the silica of the modification is received The particle diameter of rice grain is 3-30nm, more preferably 10-30nm.
According to the present invention, the nano SiO 2 particle as the modification of the nanometer sealing agent can use ability The conventional method in domain is made, it is preferable that the preparation method of the nano SiO 2 particle of the modification：
(1) in the presence of monohydric alcohol and coupling agent, by the one or more and formula (2) in the monomer of structure shown in formula (1) One or more in the monomer of shown structure carry out haptoreaction with nano SiO 2 particle；
(2) in the presence of redox initiation system, the catalytic product is subjected to polymerisation.
According to the present invention, above-mentioned formula (1) and formula (2) and the group that is directed to are as described in above, herein no longer Repeat.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, in step (1), to formula (1) and There is no particular limitation for the dosage of the monomer of structure shown in formula (2), can be received according to the silica of modification as described above Rice grain is selected, such as in order to which the acrylic acid that the construction unit with certain mol proportion described above is formed is made Analog copolymer chain and in order to obtain the acrylic copolymer chain of appropriate molecular weight described above, under considering, Preferably, the mol ratio of the dosage of the monomer of structure shown in the monomer of structure shown in formula (1) and formula (2) is 1：0.5-5, more preferably For 1：1-2, it is still more preferably 1：1.3-1.6 most preferably 1：1.5-1.6.Such as in order to enable to the modification of gained Nano SiO 2 particle on the acrylic copolymer chain described above that is modified with, it is preferable that with the dioxy On the basis of total dosage of the monomer of structure shown in the monomer of structure shown in SiClx nano particle, formula (1) and formula (2), the formula (1) Total dosage of the monomer of structure shown in the monomer and formula (2) of shown structure is more than 60 weight %, preferably more than 80 weight %, It is still more preferably 90-98 weight %, most preferably 90-95 weight %, in other words, institute more preferably more than 90 weight % The dosage for stating nano SiO 2 particle is below 40 weight %, preferably below 20 weight %, more preferably 10 weight % with Under, it is still more preferably 2-10 weight %, for example, 5-10 weight %.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, the silica nanometer The size of grain can carry out appropriate selection according to the size of the nano SiO 2 particle of required modification, it is preferable that described The particle diameter of nano SiO 2 particle is 3-30nm, more preferably 10-30nm.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, in step (1), by idol In the presence of joining agent, first by one kind in the monomer of structure shown in the one or more and formula (2) in the monomer of structure shown in formula (1) Or it is a variety of (such as mode of mixing) is contacted with nano SiO 2 particle, enable to nano SiO 2 particle through idol The effect of connection agent forms active graft site, and with the monomer of structure shown in the monomer of structure shown in formula (1) and formula (2) fully Contact, and the haptoreaction is in the presence of the monohydric alcohol, can reasonably control such haptoreaction and control with The speed of polymerisation afterwards, enabling the acquisition present invention is required to be not easy to be agglomerated into larger particles and have good seal-off effect The nano SiO 2 particle of the modification of matter.
Wherein, to the species of the monohydric alcohol, there is no particular limitation, as long as can reach the effect above, preferably Ground, the monohydric alcohol be methanol, ethanol, normal propyl alcohol and isopropanol in one or more, more preferably isopropanol, normal propyl alcohol and One or more in ethanol.The dosage of the monohydric alcohol is also limited without special, as long as can control and optimize described connect Touch and react with the speed of polymerisation to obtain by the chain modified nano SiO 2 particle of acrylic copolymer.It is preferred that The weight ratio of ground, the nano SiO 2 particle and the dosage of the monohydric alcohol is 1：5-30, more preferably 1：8-25, more enter One step is preferably 1：10-20, such as 1：15-20.
Wherein, to the species of the coupling agent, there is no particular limitation, if the effect above can be reached, such as can Think the one or more in silane coupler etc., preferably silane coupler, more preferably gamma-aminopropyl-triethoxy-silane (also referred to as KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (also referred to as KH560), γ-(methacryl Oxygen) propyl trimethoxy silicane (also referred to as KH570) and N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane (can also claim Make KH792) in one or more.The dosage of the coupling agent is also limited without special, as long as enabling to silica Nano particle suitably activates, and obtains the appropriate site that can be grafted the acrylic copolymer chain.Preferably, it is described Nano SiO 2 particle and the weight ratio of the dosage of the coupling agent are 100：0.2-10, more preferably 100：0.4-5, more enter One step is preferably 100：1-4, most preferably 100：1.2-3 such as 100：1.2-2.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, although the embodiment party of step (1) Formula can be by the list of structure shown in the one or more and formula (2) in the monomer of structure shown in monohydric alcohol, coupling agent, formula (1) One or more in body are added to the mode in reaction system together with nano SiO 2 particle, or any substep mixes The mode being mixed together again, to this present invention, there is no particular limitation.But it is to be able to so that the haptoreaction and polymerization More preferably modified nano SiO 2 particle can be obtained after reaction, under preferable case, step (1) includes：First will The monomer of structure shown in the monomer of structure shown in the formula (1) and formula (2) is mixed (such as in 10-40 DEG C of (preferably 20-30 DEG C) under, 10-40min (preferably 20-30min) is stirred under 200-500rpm (preferably 250-350rpm) rotating speed), and adjust The pH of gained mixture to 7-9, preferably 7-8, more preferably 7-7.5 (such as sodium hydroxide, potassium hydroxide, hydrogen can be used One or more in lithia etc. are adjusted)；Then again in the presence of monohydric alcohol and coupling agent, by the mixture and dioxy SiClx nano particle carries out the haptoreaction.For the operation suitable for situ of drilling well, it is highly preferred that step (1) includes：It is made The mixture (hereinafter referred to as mixture A) of the monomer of structure shown in the monomer of structure shown in above-mentioned formula (1) and formula (2)；Institute is made State mixture (the hereinafter referred to as mixture B, such as in 10-40 DEG C of (preferably 20- of monohydric alcohol and the nano SiO 2 particle 30 DEG C) under, under 200-500rpm (preferably 250-350rpm) rotating speed stir 10-40min (preferably 20-30min))；Again will Mixture A and mixture B mixing be made mixture C (such as under 10-40 DEG C (preferably 20-30 DEG C), in 200-500rpm 10-40min (preferably 20-30min) is stirred under the rotating speed of (preferably 250-350rpm))；Again in the presence of coupling agent, by mixture C carries out the haptoreaction.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, under preferable case, step (1) In, the catalytic condition includes：Temperature is 10-40 DEG C (being preferably 20-30 DEG C), and the time is that 10-60min (is preferably 20-30min)。
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, in step (2), in the oxygen Under the initiation for changing reduction initiating system, the monomer of structure shown in the monomer of structure shown in formula (1) and formula (2) is enabled to occur altogether It is poly-, and be grafted on nano SiO 2 particle so as to be made by the titanium dioxide of the modification of aforesaid propylene acid copolymer chain grafting Nano silicon particles.Usually, acrylic copolymer chain of the invention can be understood as linear polymer chain, but the present invention is simultaneously It is non-limiting in this.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, to the Redox Initiator There is no particular limitation for the species of system, as long as above-mentioned purpose can be realized, under preferable case, and the Redox Initiator Reducing agent in system is sodium hydrogensulfite.Under preferable case, the oxidant in the redox initiation system is persulfuric acid Ammonium.Wherein, the mol ratio of the reducing agent and oxidant is preferably 1：1-5, more preferably 1：2.5-3.To the redox There is no particular limitation for the dosage of initiation system, as long as can obtain, the present invention is required to be linked by aforesaid propylene acid copolymer The nano SiO 2 particle of the modification of branch, under preferable case, relative to the monomer and formula of structure shown in 1mol formula (1) (2) total dosage of the monomer of structure shown in, the dosage of the redox initiation system is 0.05-1g, more preferably 0.07- 0.8g, it is still more preferably 0.1-0.4g, more preferably 0.14-0.3g, for example, 0.2-0.28g.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, under preferable case, step (2) In, the condition of the polymerisation includes：Temperature is 40-80 DEG C (preferably 50-70 DEG C, such as 60 DEG C), and the time is that 3-6h is (excellent Elect 4-5h as).The polymerisation can also be carried out under agitation, such as be carried out under 200-400rpm mixing speed.
According to the present invention, in the preparation method of the nano SiO 2 particle of the modification, in order to by above-mentioned modification Nano SiO 2 particle extracted from the reaction system of the polymerisation, this method can also include will it is described gather Close reacted product (such as at 50-80 DEG C, 5-20h is dried at preferably 60-70 DEG C) is dried and crushes, to obtain State modified nano SiO 2 particle.Here directly the product after polymerisation is dried and crushed, the crushing of gained Particle afterwards can be used as being used as nanometer sealing agent in drilling fluid.Therefore, as the product obtained by the above method directly as modification Nano SiO 2 particle both included on nano SiO 2 particle the titanium dioxide of acrylic copolymer chain in grafting Silicon grain, includes the nano SiO 2 particle that acrylic copolymer is coated with particle again, and it is other some can The polymerization situation of energy.
According to the present invention, the bionical solid wall agent mechanism of action is as follows：The byssus line of marine organisms mussel can be in water ring Rock surface is attached under border securely, and a kind of special amino acid derivativges-dopamine contained in byssus protein is demonstrate,proved Bright is the key that mussel byssus line has strong underwater Adhesion property.When byssus protein is secreted into marine rock table by mussel from vivo During face, byssus protein passes through Fe in DOPA amine groups and seawater3+Ion crosslinks curing reaction, sticks by force so as to be formed to have The byssus line of property and cohesive force, rock surface is adhered to by mussel.Imitate the bionical solid wall agent of mussel adhesion protein Structural Development It can contact and adsorb on mud shale surface with the mud shale borehole wall with drilling fluid, and pass through DOPA amine groups and mud shale surface Fe3+Complexing, form a layer thickness in borehole wall surface crosslinking curing as 100 μm of -1mm (polymer concentration in drilling fluid Increase and increase) the polymer film with stronger adhesion.The polymer film can not only effectively prevent drilling fluid to stratum Infiltration, and there is some strength, Hydrogeochemical anomaly that can be suffered by partial offset rock, so as to play closure borehole wall mud shale Hole and the effect for improving mud shale intensity.
A preferred embodiment of the invention, the bionical solid wall agent contain the construction unit shown in formula (I)：
In formula (I), R1For hydrogen,-CH2COOR3’、-CH2COOR3, R2For hydrogen,And R1And R2At least one of beN be more than 1 integer, n R5It is each independently H or group and n R from dopamine5In At least one is the group from dopamine, R4For H or C1-C10Alkyl, R " ' is H ,-CH2COOR3' or-CH2COOR3, and R1 And R " ' it is different when be H, R3' it is hydrogen or alkali metal, R3For the group from dopamine.
The weight average molecular weight of the bionical solid wall agent can be 20000g/mol-150000g/mol, preferably 50000g/ mol-100000g/mol。
In accordance with the present invention it is preferred that in formula (I), R4For C2-C10Alkyl, more preferably C2-C6Alkyl.R4Tool Style includes but is not limited to：Ethyl, propyl group, isopropyl, butyl.
According to a kind of embodiment of the present invention, the bionical solid wall agent is prepared by the method comprised the steps of Obtain：
(1) polymer and formula that will contain the construction unit shown in formula (III) are R4CH=CHCOOH unsaturated carboxylic Acid carries out graft copolymerization；
(2) polymer obtained by step (1) and dopamine and/or Dopamine hydrochloride are subjected to condensation reaction；
R ' and R " is each independently H or-CH2COOR3', and be H, R when R ' and R " is different3' it is hydrogen or alkali metal；R4For H or C1-C10Alkyl.
In the preparation process of above-mentioned bionical solid wall agent, the condition of the graft copolymerization described in step (1) can wrap Include：Temperature is 50-90 DEG C, preferably 60-80 DEG C；Time is 1-10 hours, preferably 2-6 hours；Containing shown in formula (III) The mol ratio of the dosage of dosage and unsaturated carboxylic acid of the polymer of construction unit in terms of hydroxyl can be 1：0.1-4；Preferably 1：0.5-3；The graft copolymerization can be carried out in the presence of initiator, initiator can be ammonium ceric nitrate, potassium peroxydisulfate, One or more in ammonium persulfate.
The polymer of the construction unit containing shown in formula (III) is particularly preferably carboxymethyl chitosan.The carboxylic first Base enclosure glycan is contacted with unsaturated carboxylic acid mixing preferably in the form of its aqueous solution and carries out graft copolymerization.Carboxymethyl chitosan Sugar aqueous solution can be by by carboxymethyl chitosan (weight average molecular weight can be 10000g/mol-80000g/mol)) stirring Under (mixing speed can be 100-500 revs/min) be dissolved in the water to obtain.As long as the dosage of water meets carboxymethyl chitosan Sugar is completely dissolved, it is preferable that the weight of carboxymethyl chitosan and water ratio can be 1：20-50.
The unsaturated carboxylic acid can be the unsaturated monocarboxylic acid that carbon number is more than 3, the unsaturated carboxylic acid Carbon number is preferably 3-11, more preferably 3-7.The specific example of the unsaturated carboxylic acid include but is not limited to acrylic acid and/ Or methacrylic acid.
In the preparation process of above-mentioned bionical solid wall agent, the condition of the condensation reaction described in step (2) can include：Temperature Spend for 10-50 DEG C, preferably 20-40 DEG C；Time is 2-48 hours, preferably 6-36 hours.Polymer obtained by step (1) The dosage of (in terms of carboxyl) can be 1 with the mol ratio of dopamine and total dosage of Dopamine hydrochloride (in terms of amido)：0.01- 0.2, preferably 1：0.02-0.1.The condensation reaction can be carried out in the presence of a catalyst, the catalyst can be 1- ethyls- (3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate and/or N, N'- DIC.
According to the present invention, the bionical shale control agent has high positive charge density and easily enters mud shale nano grade pore Gap is simultaneously adsorbed on clay mineral surface, so as to preferably compress surface of clay electric double layer, reduce clay swell pressure, is prevented The borehole well instability caused by clay swell.In addition, pass through by the bionical shale control agent that raw material is researched and developed of biological vivo acid After the rejected well drilling liquid landfill disposal in later stage, biodegradation can be carried out within a short period of time, and there is good environmental-protecting performance.From And can preferably coordinate the nanometer sealing agent in the drilling fluid and bionical solid wall agent, when in for water-base drilling fluid, promote Enter the raising of the temperature resistance of drilling fluid of gained, seal-off effect and inhibition, and beneficial to obtaining highdensity drilling fluid, moreover it is possible to keep The higher feature of environmental protection.
According to the present invention, the weight average molecular weight of the bionical shale control agent is 800-4000g/mol, preferably 1550- 4000g/mol, more preferably 1600-3300g/mol.By the way that the weight average molecular weight of the bionical shale control agent of the present invention is controlled Within the above range, the bionical shale control agent can be made to diffuse into the page that buried depth is more than more than 2000 meters well Rock stratum average pore size in the pore within the scope of 4-10nm, and bionical shale control agent mud shale surface have it is higher Adsorbance and adsorption strength.In addition, when the weight average molecular weight of the bionical shale control agent is higher than 4000g/mol, there is hardly possible To diffuse into shale formation average pore size of the buried depth more than more than 2000 meters in the pore within the scope of 4-10nm Problem.And when the weight average molecular weight of the bionical shale control agent is less than 800g/mol, its absorption to mud shale surface is strong Spend insufficient.The profile exponent Mw/Mn of the molecular weight of the bionical shale control agent for example can be 1.5-3.
According to the present invention, formula (3)Shown construction unit has arginic main body Chemical constitution, formula (4)Shown construction unit has the main body chemical constitution of lysine, therefore, actual Upper bionical shale control agent of the invention is a kind of binary polyaminoacid (i.e. the condensation peptide of arginine and lysine).The present invention's So the bionical shale control agent of the present invention is formed from the construction unit shown in formula (3) and the construction unit shown in formula (4), It is because on the one hand, the construction unit shown in construction unit and formula (4) shown in formula (3) is the structure of amino acid, is readily able to Degraded by Institute of Micro-biology, therefore a kind of " bionical shale control agent " can be defined as；On the other hand, the structure list shown in formula (3) Member has three sites that can form nitrogen cation (such as), the structure shown in formula (4) Unit has a site that can form nitrogen cation (such as), so as to pass through the knot shown in by formula (3) The combination of construction unit shown in structure unit and formula (4) can form the superior shale inhibition with suitable cation amount The bionical shale control agent of energy.The present invention the construction unit shown in above-mentioned formula (3) and the construction unit shown in formula (4) to being made up of The end of bionical shale control agent be not particularly limited, can be conventional group, such as H, hydroxyl or salt of formation etc..
According to the present invention, although the bionical shale control agent as long as there is weight average molecular weight in 800-4000g/mol In the range of, and be made up of the construction unit shown in the formula (3) of specific molar ratio and the construction unit shown in formula (4), still In order to ensure that the bionical shale control agent preferably plays shale inhibition energy and is then able to preferably by Institute of Micro-biology Degraded, it is preferable that the mol ratio of the construction unit shown in construction unit and formula (4) shown in formula (3) is preferably 0.3-5：1, more Preferably 1-5：1, more preferably 1-4：1, most preferably 2-4：1.From the formula (3) with above-mentioned preferred molar ratio Suo Shi Construction unit and formula (4) shown in construction unit form bionical shale control agent can preferably cause the bionical shale The construction unit shown in formula (3) in inhibitor and the construction unit shown in formula (4) synergistically help the bionical shale and suppressed Agent is volatilized its shale inhibition and biodegradability, and with being of relatively low cost.
The present invention is not particularly limited to the structure of the binary polyaminoacid, can be well-regulated block copolymer, The well-regulated block copolymer in part and random copolymer, in order to avoid cumbersome production technology, bionical shale of the invention suppression Preparation is preferably random copolymer.
According to a kind of embodiment of the present invention, the preparation method of the bionical shale control agent includes：Inorganic In the presence of acid catalyst, by arginine and lysine progress condensation reaction, the dosage of the arginic dosage and lysine Mol ratio is 0.2-6：1, the weight average molecular weight that the condensation reaction condition makes obtained bionical shale control agent is 800- 4000g/mol。
According to the present invention, in the preparation method of the bionical shale control agent, the arginine can be L-type, D types Or two kinds of mixture, the lysine can be L-type, D types or two kinds mixture.It is preferred that using L-arginine and 1B.
According to the present invention, in the preparation method of the bionical shale control agent, to the use of the arginine and lysine Amount does not limit especially, as long as the weight average molecular weight for enabling to the product of the condensation reaction is 800-4000g/mol , it is preferable that the mol ratio of the arginic dosage and the dosage of lysine is 0.3-0.5：1, preferably 1-5：1, more Preferably 1-4：1, most preferably 2-4：1.
According to the present invention, in the preparation method of the bionical shale control agent, the condensation reaction is in inorganic acid catalysis Carried out in the presence of agent.Why the application uses inorganic acid catalyst rather than alkali compounds as catalyst, a mesh Be the condensation reaction for promoting arginine and lysine progress, the bionical shale that the present invention with higher yield is made suppresses Agent, but again the molecular weight of condensation reaction resulting polymers can be avoided excessive simultaneously；Another purpose is gathered in order that obtaining gained Compound carries nitrogen cation to a greater extent, so as to provide cation for bionical shale control agent.The inorganic acid catalyst tool Body can be at least one of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid that concentration is 1-6mol/L, and preferably phosphoric acid (such as can be with For 85-98 weight % concentrated phosphoric acid).When the inorganic acid catalyst preferably uses phosphoric acid, this can be made in more high yield The bionical shale control agent of invention.
According to the present invention, in the preparation method of the bionical shale control agent, it is preferable that the inorganic acid catalyst Dosage is 1 with the mol ratio of arginine and total dosage of lysine：0.3-3, more preferably 1：0.4-3.
According to the present invention, in the preparation method of the bionical shale control agent, it is preferable that the inorganic acid catalyst is Phosphoric acid, and the dosage of phosphoric acid and the mol ratio of arginine and total dosage of lysine are 1：2-3, it can so obtain more particularly suitable Weight average molecular weight bionical shale control agent.
According to the present invention, in the preparation method of the bionical shale control agent, bar of the present invention to the condensation reaction Part does not limit especially, is as long as weight average molecular weight can be made under the arginine of the present invention and the mol ratio of lysine 800-4000g/mol bionical shale control agent, the condition of the conventional synthesizing amino acid polymer in this area can be used, Such as carry out condensation reaction under arginine and lysine molten state, it is preferable that the condition of the condensation reaction includes：Temperature For 180-230 DEG C, time 4-20h.It is highly preferred that the condition of the condensation reaction includes：Temperature is 195-215 DEG C, the time For 8-16h.
According to the present invention, in the preparation method of the bionical shale control agent, bionical shale provided by the invention suppresses The preparation method of agent is additionally may included in after the condensation reaction terminates, by the pH value of the mixture obtained by condensation reaction adjust to 6-7.In such a case, it is possible to adjust pH value using any alkali compounds, such as alkali metal hydroxide can be used (such as Sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal oxide (such as sodium oxide molybdena, potassium oxide, lithia), alkali carbonate At least one of (such as sodium carbonate, potassium carbonate, lithium carbonate), alkali metal hydrogencarbonate (such as sodium acid carbonate, saleratus). Above-mentioned alkali compounds can be used in the form of its solution, can also (such as powder, particle etc., such as hydrogen in solid form Sodium oxide molybdena powder) use.Preferably, the alkali compounds is used in the form of its solution, it is highly preferred that the alkaline chemical combination The concentration of the solution of thing is 1-10mol/L.The solution of the alkali compounds is more preferably the water of 3-5mol/L sodium hydroxide Solution, the aqueous solution of potassium hydroxide or the aqueous solution of saturated sodium carbonate that concentration is 3-5mol/L.According to the present invention, in order to obtain Polymer obtained by the condensation reaction, the above method can also include to regulation pH value after solution concentrated, dry and Crush.
According to the present invention, in the preparation method of the bionical shale control agent, bionical shale provided by the invention suppresses The preparation method of agent further preferably after completion of the reaction, is adding water progress dissolving step when temperature is down to below 125 DEG C, separates institute Obtain the aqueous solution and dry obtained solid, then gained solid is redissolved in dimethyl sulfoxide, gained liquid is evaporated and produces this The bionical shale control agent of invention.
According to the present invention, the above-mentioned addition of the water-base drilling fluid (being also referred to as Environment-protecting Drilling Fluids below) containing the present invention Agent, poor higher temperature resistance, seal-off effect and inhibition can be obtained, and it is higher close to be that filler obtains after coordinating Degree, the shale gas of bad ground is included especially suitable for exploitation.Under preferable case, relative to the drilling fluid of 100 parts by weight In water, the total content of the nanometer sealing agent, bionical solid wall agent and bionical shale control agent is below 10 parts by weight, more preferably Below 8 parts by weight, still more preferably for 6 parts by weight below.Meeting in this case, relative to described in 100 parts by weight Water in drilling fluid, it is preferable that the content of the nanometer sealing agent be 5 parts by weight below (preferably below 3 parts by weight, more preferably 2 Below parts by weight, for example, 1-2 parts by weight), the dosage of the bionical solid wall agent for below 5 parts by weight (preferably 3 parts by weight with Under, more preferably below 2 parts by weight, still more preferably 0.5-2 parts by weight, for example, 0.5-1 parts by weight), the bionical shale The dosage of inhibitor be 5 parts by weight below (preferably below 3 parts by weight, more preferably below 2 parts by weight, still more preferably 0.5-2 Parts by weight, for example, 0.5-1 parts by weight).
According to the present invention, the environment-friendly type water base drilling fluid can also contain the conventional addition being used in water-base drilling fluid Agent, in order to obtain suitable density, the drilling fluid also contains filler, and it by weight ratio is 1 that the filler, which is,：0.55- 6：The calcium carbonate composition of 0.55-6 1600-2500 mesh, 1050-1500 mesh and 500-1000 mesh.Preferably, the filler is It is 1 by weight ratio：1-2：The calcium carbonate composition of 1-2 1900-2200 mesh, 1000-1240 mesh and 720-920 mesh.Relative to 100 Water in the drilling fluid of parts by weight, it is preferable that the content of the filler is 1-5 parts by weight, more preferably 2-4 weight Part.
According to the present invention, the environment-friendly type water base drilling fluid can also contain for other routines in water-base drilling fluid Additive, under preferable case, the drilling fluid is also containing one in tackifier, fluid loss additive, anti-sloughing agent, lubricant and heavy weight additive etc. Kind is a variety of.
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.Relative to the water in the drilling fluid of 100 parts by weight, it is highly preferred that the increasing The content of stick is 0.1-0.5 parts by weight, more preferably 0.1-0.2 parts by weight.
Wherein, the fluid loss additive has the function that certain anti-collapse closure and filtrate reducing, such as can be modified starch, sulphur Change the one or more in pitch etc., preferably modified starch.It is more excellent relative to the water in the drilling fluid of 100 parts by weight Selection of land, the content of the fluid loss additive is 1-5 parts by weight, more preferably 2-4 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.Relative to the water in the drilling fluid of 100 parts by weight, it is highly preferred that the anti-sloughing agent Content be 1-5 parts by weight, more preferably 2-4 parts by weight.
Wherein, the lubricant 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), preferably FK-10.Relative to 100 parts by weight Water in the drilling fluid, it is highly preferred that the content of the lubricant is 1-5 parts by weight, more preferably 2-4 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.
According to the present invention, the environment-friendly type water base drilling fluid can obtain higher higher heat-resisting property, higher seal-off effect And inhibition, and higher density can be obtained, such as the drilling fluid has anti-more than 120 DEG C heat-resisting property, its density is 2.3g/cm3(the front and rear density of heat rolling can keep being basically unchanged) above.
The present invention will be described in detail by way of examples below.
In following examples and comparative example：Weight average molecular weight and molecular weight distributing index are using (the experiment of GPC gel chromatographies Instrument be waters companies of the U.S. gel permeation chrommatograph, model E2695) measure.The modification being scattered in drilling fluid The particle diameter distribution of nano SiO 2 particle group is that (Britain's Malvern instrument has using Zeta point positions and laser particle size analyzer Limit company) measure.SEM figures are measured using Hitachi, Ltd F20 Flied emission transmission electron microscopes.Copolymer chain Content refer to that the content of copolymer in the product of gained accounts for the percentage by weight of whole product.Filler be by weight ratio be 1： 1：1 2000 mesh, 1200 mesh and 800 mesh calcium carbonate granules are formed.
Nanometer sealing agent preparation example 1
(1) 0.12mol acrylic acid and 0.19mol N, N '-methylene-bisacrylamide (are purchased from Huantai County's thyrite Work Co., Ltd) at about 25 DEG C, stir 30min under 300rpm rotating speed, and adjust pH to 7 with sodium hydroxide, mixed Thing A1；By 0.5g nano SiO 2 particle (being purchased from the Nanjing Tian Hang new materials Co., Ltd TSP trades mark, particle diameter is about 20nm) 30min is stirred at about 25 DEG C, under 300rpm rotating speed with 8g isopropanol, obtains mixture B1；By mixture A1 and mixing Thing B1 is at about 25 DEG C, stirs 30min under 300rpm rotating speed, obtains mixture C 1；
(2) by 0.01g coupling agent gamma-aminopropyl-triethoxy-silane (purchased from thyrite Chemical Co., Ltd. of Huantai County The KH550 trades mark) and said mixture C1 mixing and at 60 DEG C, 200rpm stirring under react 30min；Then add 0.094g's Redox initiation system (is 1 by mol ratio：2.5 sodium hydrogensulfite and ammonium persulfate composition) and continue at 60 DEG C, 200rpm stirrings are lower to carry out polymerisation 4h；
(3) product of above-mentioned polymerisation is dried overnight (about 24h) at 70 DEG C, and crushed, obtain modified dioxy SiClx nano particle S1.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, on the nano SiO 2 particle S1 of the modification, have by Mol ratio is 1：Construction unit (the R of structure shown in 1.5 formula (1-a)1Selected from-OH) and formula (2-a) shown in structure structure list (L is-CH to member2-) the atactic propene acid copolymer chain that forms, the content of the copolymer chain is 92 weight %, weight average molecular weight About 650000g/mol；The nano SiO 2 particle S1 of modification particle diameter is about 23nm, and its SEM schemes as shown in Figure 1.
Nanometer sealing agent preparation example 2
(1) it is 0.15mol methyl acrylate and 0.2mol N, N '-methylene-bisacrylamide is (safe purchased from Huantai County Sharp Chemical Co., Ltd.) at about 30 DEG C, stir 25min under 250rpm rotating speed, and adjust pH to 7.5 with sodium hydroxide, obtain To mixture A2；1g nano SiO 2 particle (is purchased from the Nanjing Tian Hang new materials Co., Ltd TSP trades mark, particle diameter is about 20nm) isopropanol with 8g stirs 25min at about 30 DEG C, under 250rpm rotating speed, obtains mixture B2；By mixture A2 and Mixture B2 is at about 30 DEG C, stirs 25min under 250rpm rotating speed, obtains mixture C 2；
(2) by 0.012g coupling agent gamma-aminopropyl-triethoxy-silane (purchased from thyrite Chemical Co., Ltd. of Huantai County The KH550 trades mark) and said mixture C2 mixing and at 50 DEG C, 250rpm stirring under react 30min；Then add 0.094g's Redox initiation system (is 1 by mol ratio：3 sodium hydrogensulfite and ammonium persulfate composition) and continue at 50 DEG C, 200rpm stirrings are lower to carry out polymerisation 5h；
(3) product of above-mentioned polymerisation is dried overnight (about 24h) at 70 DEG C, and crushed, obtain modified dioxy SiClx nano particle S2.
Through infrared, proton nmr spectra and carbon spectrum analysis detection, on the nano SiO 2 particle S2 of the modification, have by Mol ratio is 1：Construction unit (the R of structure shown in 1.33 formula (1-a)1Selected from methoxyl group) and formula (2-a) shown in structure knot (L is-CH to structure unit2-) form atactic propene acid copolymer chain, the content of the copolymer chain is 94 weight %, is divided equally again Son amount is about 720000g/mol；The nano SiO 2 particle S2 of modification particle diameter is about 26nm.
Nanometer sealing agent prepares comparative example 1
According to the method described in nanometer sealing agent preparation example 1, the difference is that, N, N '-di-2-ethylhexylphosphine oxide are not used in step (1) Acrylamide, and the dosage of acrylic acid increases to 0.3mol；So as to which modified nano SiO 2 particle DS1 be made after three steps.
Detect through infrared, proton nmr spectra and carbon spectrum analysis, on the nano SiO 2 particle DS1 of the modification, have Construction unit (the R of structure shown in formula (1-a)1Selected from-OH) formed atactic polymer chain, the content of the polymer chain is 98 weights % is measured, weight average molecular weight is about 1200000g/mol；The nano SiO 2 particle DS1 of modification particle diameter is about 40nm.
Nanometer sealing agent prepares comparative example 2
According to the method described in nanometer sealing agent preparation example 1, the difference is that, step does not use acrylic acid, and N in (1), The dosage of N '-methylene-bisacrylamide increases to 0.3mol；So as to which modified nano SiO 2 particle be made after three steps DS2。
Detect through infrared, proton nmr spectra and carbon spectrum analysis, on the nano SiO 2 particle DS2 of the modification, have (L is-CH to the construction unit shape of structure shown in formula (2-a)2-) into atactic polymer chain, the content of the polymer chain is 96 weights % is measured, weight average molecular weight is about 120000g/mol；The nano SiO 2 particle DS2 of modification particle diameter is about 42nm.
Bionical solid wall agent preparation example 1
(1) 1000kg deionized waters are added in container, (200 revs/min of rotating speed) adds carboxymethyl chitosan (purchase under stirring From Beijing crop field Feng Tuo chemical technologies Co., Ltd, there is the structure shown in formula (III), weight average molecular weight 52000g/mol, Degree of substitution by carboxymethyl is 1.4) 50kg, continues stirring after charging until carboxymethyl chitosan all dissolves, does not wad a quilt with cotton substantially Shape solid is suspended in solution.
(2) acrylic acid 50kg is added into carboxymethyl chitosan sugar aqueous solution, stirs 5 minutes, then adds nitric acid 2kg, after Continuous stirring 5 minutes, until carboxymethyl chitosan, acrylic acid and salpeter solution are well mixed.Then ammonium ceric nitrate 4kg is added, is stirred Mix until ammonium ceric nitrate fully dissolves.Then reaction system is warming up to 70 DEG C, temperature in the kettle starts timing after reaching 70 DEG C, instead Answer 4 hours, reactor is cooled to 25 DEG C after completion of the reaction.First stage product should be light yellow transparent liquid.
(3) 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate is added into the reaction system after cooling 5kg1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (is divided into 5 parts, often input is a, stirs 15 points by 5kg Clock, then input is lower a, until all input finishes).Then it is stirred at room temperature 12 hours, until 1- ethyls-(3- dimethylaminos Base propyl group) phosphinylidyne diimmonium salt hydrochlorate is completely dissolved, and product is still light yellow transparent solution.
(4) hydrochloric acid is added into the system for having dissolved 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate Dopamine 5kg, lower reaction is stirred at room temperature 24 hours until the bionical solid wall agent GBFS-1 generations of final reacting product, it is certain to have The weak yellow liquid of viscosity.After testing, the bionical solid wall agent GBFS-1 of reaction product weight average molecular weight is 84320g/mol.
Bionical shale control agent preparation example 1
At 195 DEG C, the 1B of 0.5mol (87.1g) L-arginine and 0.2mol (29.2g) is stirred, And 1.75mol (171.5g) phosphoric acid (85 weight % phosphate aqueous solutions) is added, and react 16h at 195 DEG C.Reaction finishes After add 200g water thereto when temperature is down to 120 DEG C or so, continue stirring 20 minutes and be dissolved completely in water to product.So Afterwards, the reaction product aqueous solution is taken out and obtains solid in 120 DEG C or so drying, solid is dissolved in dimethyl sulfoxide (DMSO), passed through Suction filtration separates insoluble matter with solution.Then solution is evaporated by rotary evaporation, that is, the bionical shale for obtaining the present invention suppresses Agent YZFS-1 (91.8) g.Its weight average molecular weight M is measured by gel permeation chromatographywFor 1551g/mol, the distribution of molecular weight refers to Number is 1.465.The construction unit and formula shown in resulting polymers Chinese style (3) are understood by its proton nmr spectra, carbon spectrum analysis (4) mol ratio of the construction unit shown in is 2.47：1.
Embodiment 1
The present embodiment is used for the environment-friendly type water base drilling fluid for illustrating the present invention.
It is formulated and is：The water of 100 parts by weight, the nano SiO 2 particle S1 of the modification of 2 parts by weight, 1 parts by weight it is bionical Gu wall agent GBFS-1, the bionical shale control agent YZFS-1 of 1 parts by weight, the filler of 3 parts by weight, the polypropylene of 0.2 parts by weight Amide potassium salt (purchased from Renqiu City Hong Ze petrochemical industries Co., Ltd K-PAM, same as below), the modified starch of 3 parts by weight (is purchased from The LYS of Shandong get Shun Yuan Petroleum Technology Co., Ltd, same as below), the potassium humate of 3 parts by weight is (sincere purchased from stone Dabo, Beijing Science and Technology Ltd. trade mark KHM), the organic salt of 15 parts by weight (is purchased from the Organic Sodium Salt GD- of the wide petrochemical industry Co., Ltd in Hebei WT, same as below), the lubricant (modified phospholipid for being purchased from the Shanghai You Chuan Industrial Co., Ltd.s FHGT-G trades mark) of 2 parts by weight, The barite (being purchased from Sichuan Zheng Rong industrial corporations trade mark barite ZR-43) of 330 parts by weight；So as to which drilling fluid Y1 be made.
Embodiment 2
The present embodiment is used for the environment-friendly type water base drilling fluid for illustrating the present invention.
According to the formula described in embodiment 1, the difference is that, modification is replaced using modified nano SiO 2 particle S2 Nano SiO 2 particle S1；So as to which drilling fluid Y2 be made.
Embodiment 3
The present embodiment is used for the environment-friendly type water base drilling fluid for illustrating the present invention.
According to the formula described in embodiment 1, the difference is that, the nano SiO 2 particle S1 of the modification used is 1 weight Part, bionical solid wall agent GBFS-1 is 2 parts by weight, and bionical shale control agent YZFS-1 is 2 parts by weight；So as to which drilling fluid Y3 be made.
Comparative example 1
According to the formula described in embodiment 1, the difference is that, replace being modified using modified nano SiO 2 particle DS1 Nano SiO 2 particle S1；So as to which drilling fluid DY1 be made.
Comparative example 2
According to the formula described in embodiment 1, the difference is that, replace being modified using modified nano SiO 2 particle DS2 Nano SiO 2 particle S1；So as to which drilling fluid DY2 be made.
Comparative example 3
According to the formula described in embodiment 1, the difference is that, Nanjing (is purchased from using unmodified nano SiO 2 particle The Tian Hang new materials Co., Ltd TSP trades mark, particle diameter is about 20nm) replace modified nano SiO 2 particle S1；So as to be made Drilling fluid DY3.
Comparative example 4
According to the formula described in embodiment 1, the difference is that, bionical solid wall agent GBFS-1 is not used, so as to which drilling fluid be made DY4。
Comparative example 5
According to the formula described in embodiment 1, the difference is that, petroleum science and technology (is good for purchased from day using the small cation of 1 parts by weight Co., Ltd, trade mark CSM-1) replace bionical shale control agent YZFS-1；So as to which drilling fluid DY5 be made.
Test case 1
Drilling fluid basic performance is tested：Above-mentioned drilling fluid Y1-Y3 and DY1-DY5 be not subjected to the feelings of heat rolling processing respectively In the case of under condition and after 120 DEG C of heat rolling 16h processing, plastic viscosity (PV), apparent viscosity (AV), yield value are tested at room temperature (YP), ratio of dynamic shear force/yield value to plastic viscosity, gel strength (GEL, that is,/egress of ingressing), middle filter pressing loss (API), high temperature and high pre ssure filtration (HTHL), close Degree and pH, as a result as shown in table 1, 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 according to state using six fast viscosimeter of normal form What method specified in family standard GB/T29170-2012 measured, unit mPas,Yield value (YP) Measured using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six, YP=0.5 (2θ300-θ600), unit Pa.Ratio of dynamic shear force/yield value to plastic viscosity：The Hes of φ 600 are successively read using six fast rotation viscometers φ300。
GEL gel strengths refer to the ratio of the gel structure intensity, i.e. gel initial and 10-minute gel strength formed after drilling fluid is static, Unit is Pa/Pa；Wherein, gel initial and 10-minute gel strength are according to standard GB/T/T29170-2012 using six fast viscosimeter of normal form Specified in method measure：
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, be using high pressure high temperature filter tester according to standard GB/T/ Method measures specified in T29170-2012, unit mL.
Table 1
Note："/" represents unmeasured.
It can be seen from Table 1 that although density is larger, a large amount of barites, the drilling fluid of the present invention are contained in system System still has a preferable ratio of dynamic shear force/yield value to plastic viscosity, and filter pressing loss and high temperature and high pre ssure filtration are all smaller in API, but changes wellbore fluid After nanometer sealing agent, bionical solid wall agent and bionical inhibitor in system, the drilling fluid system (i.e. comparative example DY1-DY5) of gained Ratio of dynamic shear force/yield value to plastic viscosity is begun to decline, and illustrates that the rheological characteristic of system is deteriorated；Filter pressing loss and high temperature and high pre ssure filtration become in the API of system simultaneously Greatly, this will be unfavorable for wellbore stability.
Test case 2
Heat roll back yield key step it is as follows：It (is running water and above drilling well respectively to add 350mL test solutions in ageing can Liquid), 6-10 mesh mud shale landwaste 50g are weighed, in 120 DEG C of roller furnace, roll scattered 16h；Then will be reclaimed with 40 mesh sieves Rock sample is sieved and washed totally in water, will be tailed over rock sample and is put into surface plate, constant weight is dried in 105 DEG C of baking ovens；Weigh, by following formula Heat is calculated to roll back yield (the results are shown in Table 2)：S=M/50 × 100%
In formula：The rate of recovery after the mesh sieves of S -40, %；The screen over-size of the mesh sieves of M -40, g.
Table 2
Test solution Heat is rolled back yield/%
Running water 18.62
Drilling fluid Y1 99.12
Drilling fluid Y2 99.24
Drilling fluid Y3 99.48
Drilling fluid DY1 91.84
Drilling fluid DY2 92.12
Drilling fluid DY3 90.56
Drilling fluid DY4 76.18
Drilling fluid DY5 80.10
It can be seen from Table 2 that drilling fluid system landwaste rolling rate of recovery of the invention illustrates system more than 99% There is good inhibiting effect to mud shale, change nanometer sealing agent, bionical solid wall agent and bionical inhibitor in drilling fluid system Afterwards, the landwaste rolling rate of recovery of the drilling fluid system (i.e. comparative example DY1-DY5) of gained greatly reduces, and inhibition is deteriorated.
Test case 3
Dilatancy is measured using method of the binary channels shale expansion instrument according to described in SY/T 5613-2000, its It the results are shown in Table shown in 3, and key step is as follows：
1st, prepared by rock core：The sodium bentonite 10g dried at 105 DEG C ± 2 DEG C is weighed, loads and surveys in cylinder, and stopper rod is inserted Cylinder is surveyed, 5min is kept under pressure 10MPa.
2nd, blank test：Survey cylinder with rock core is arranged on shale expansion tester, distilled water is injected and surveys cylinder, is made It soaks rock core 16h, records the linear expansion amount of rock core.
3rd, test solution determines：Survey cylinder with rock core is arranged on shale expansion tester, takes the injection of 20mL drilling fluids to survey In cylinder, it is soaked rock core 16h, record the linear expansion amount of rock core, linear expansion reduced rate is calculated by formula：In formula, B-rock core linear expansion reduced rate, unit is percentage (%)；ΔH1- distillation water logging The linear expansion amount (i.e. rock core increases height) of rock core after bubble 16h, unit is millimeter (mm)；ΔH2- sample solution soaks 16h The linear expansion amount (i.e. rock core increases height) of rock core afterwards, unit is millimeter (mm).
Table 3
Test solution Rock core increases height/mm Rock core linear expansion reduced rate/%
Running water 8.76 /
Drilling fluid Y1 0.86 90.18
Drilling fluid Y2 0.82 90.64
Drilling fluid Y3 0.76 91.32
Drilling fluid DY1 1.24 85.84
Drilling fluid DY2 1.32 84.93
Drilling fluid DY3 1.43 83.68
Drilling fluid DY4 2.04 76.71
Drilling fluid DY5 2.49 71.58
It can be seen from Table 3 that drilling fluid system rock core linear expansion reduced rate of the invention is more than 90%, explanation The drilling fluid of the present invention has a good inhibiting effect, changes nanometer sealing agent in drilling fluid system, bionical solid wall agent and bionical After inhibitor, the rock core linear expansion reduced rate of the drilling fluid system (i.e. comparative example DY1-DY5) of gained substantially reduces, inhibition It is deteriorated.
Test case 4
The environmental-protecting performance of drilling fluid mainly by determine content of beary metal, acute biological toxicity and biodegradable come Evaluated.
Content of beary metal comparative evaluation：Above-mentioned drilling fluid filtrate is carried out using atomic fluorescence detector, plasma mass spectrometry Content of beary metal is evaluated, and the results are shown in Table shown in 4, wherein, table 4 gives GB4284-84《Pollutant catabolic gene mark in agricultural sludge It is accurate》In Heavy Metals content standard requirement limit value (see standard value row).Acute biological toxicity comparative evaluation：Using Microtoxic determination of acute toxicity instrument, determine the acute biological toxicity EC of above-mentioned drilling fluid filtrate50, the results are shown in Table shown in 4. Biodegradable comparative evaluation：BODTrack Quick testing instruments are respectively adopted and COD analyzers determine drilling fluid filtrate BOD5With CODcr values, BC values (i.e. BOD is then calculated5/ CODcr), it the results are shown in Table shown in 4.
Table 4
Note：EC50Acute biological toxicity value；BOD5The biodegradable sex index of/CODcr；BOD5- 5d BODs, mg·L-1；CODcr chemical oxygen consumption (COC)s mgL-1
As can be seen from Table 4, content of beary metal is low, acute biological malicious in the Environment-protecting Drilling Fluids system of present invention gained (industry requirement is EC to property50More than 30000mgkg-1) and biodegradable (industry requirement is BOD5/ CODcr is more than 0.1) contrast drilling fluid will be better than, while will be far better than the standard requirement of industry, so the drilling fluid tool of present invention gained There is the preferable feature of environmental protection.
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 (36)

1. a kind of water-base drilling fluid, it is characterised in that the drilling fluid contains a nanometer sealing agent, bionical solid wall agent, the suppression of bionical shale Preparation and filler,
The nanometer sealing agent is modified nano SiO 2 particle, the modification on the nano SiO 2 particle of the modification Group includes acrylic copolymer chain, the structure as shown in following formula (1) of the construction unit in the acrylic copolymer chain One or more offers in the monomer of structure shown in one or more and formula (2) in monomer；The acrylic copolymer In thing chain, the structure list of the monomer offer of structure shown in the construction unit and formula (2) of the monomer offer of structure shown in the formula (1) The mol ratio of member is 1：0.5-5；The weight average molecular weight of the acrylic copolymer chain is 100000-1500000g/mol；
Wherein, R1Selected from-OH, C1-C10 alkoxy or-N (R3)R2, R2And R3It is each independently selected from H, C1-C10 alkyl With the C1-C10 alkyl being substituted with a substituent, the substituent is-COOH ,-OH, halogen and-SO3One or more in H； L is C0-C10 alkylidene；
The bionical solid wall agent is that the carboxymethyl chitosan of the group from dopamine is grafted with main chain, described to be derived from dopamine Group such as formula (I-1) shown in：
The bionical shale control agent is made up of the construction unit shown in formula (3) and the construction unit shown in formula (4)：
The mol ratio of the construction unit shown in construction unit and formula (4) shown in formula (3) is 0.2-6：1, and the bionical shale The weight average molecular weight of inhibitor is 800-4000g/mol；
The filler be by weight ratio be 1：0.55-6：0.55-6 1600-2500 mesh, 1050-1500 mesh and 500-1000 Purpose calcium carbonate forms.
2. drilling fluid according to claim 1, wherein, the nanometer sealing agent, the bionical solid wall agent and described bionical The weight ratio of shale control agent is 100：20-500：20-500.
3. drilling fluid according to claim 2, wherein, the nanometer sealing agent, the bionical solid wall agent and described bionical The weight ratio of shale control agent is 100：30-300：30-300.
4. drilling fluid according to claim 3, wherein, the nanometer sealing agent, the bionical solid wall agent and described bionical The weight ratio of shale control agent is 100：50-200：50-200.
5. according to the drilling fluid described in any one in claim 1-4, wherein, the structure in the acrylic copolymer chain The construction unit of structure shown in one or more and formula (2-a) in unit construction unit of structure as shown in following formula (1-a) In one or more compositions：
6. according to the drilling fluid described in any one in claim 1-4, wherein, R1Alkoxy or-N selected from-OH, C1-C6 (R3)R2, R2And R3The C1-C6 alkyl for being each independently selected from H, C1-C6 alkyl and being substituted with a substituent, the substituent For-COOH ,-OH and-SO3One or more in H；L is C1-C6 alkylidene.
7. drilling fluid according to claim 6, wherein, R1Selected from-OH, C1-C4 alkoxy or-N (R3)R2, R2And R3Respectively From the alkyl independently selected from H, C1-C4 and the alkyl for the C1-C4 being substituted with a substituent, the substituent be-COOH ,-OH and- SO3One or more in H；L is C1-C4 alkylidene.
8. drilling fluid according to claim 7, wherein, R1Selected from-OH, methoxyl group, ethyoxyl, propoxyl group or-N (R3)R2, R2And R3Be each independently selected from H, methyl, ethyl, propyl group, isopropyl, isobutyl group, the tert-butyl group, the methyl being substituted with a substituent, The ethyl that is substituted with a substituent, the propyl group being substituted with a substituent, the isopropyl being substituted with a substituent, the isobutyl being substituted with a substituent Base and the tert-butyl group being substituted with a substituent, the substituent in the alkyl of the substituted C1-C4 is-COOH and/or-SO3H；L For-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2- or-CH2- CHCH3-CH2-。
9. according to the drilling fluid described in any one in claim 1-4 and 7-8, wherein, in the acrylic copolymer chain, The construction unit that the monomer of structure shown in the construction unit and formula (2) that the monomer of structure shown in the formula (1) provides provides rubs You are than being 1：1-2.
10. drilling fluid according to claim 1, wherein, the weight average molecular weight of the acrylic copolymer chain is 120000-1400000g/mol。
11. drilling fluid according to claim 9, wherein, using the gross weight of the nano SiO 2 particle of the modification as Benchmark, the content of the acrylic copolymer chain is more than 60 weight %.
12. drilling fluid according to claim 11, wherein, using the gross weight of the nano SiO 2 particle of the modification as Benchmark, the content of the acrylic copolymer chain is more than 80 weight %.
13. drilling fluid according to claim 9, wherein, the particle diameter of the nano SiO 2 particle of the modification is 3- 30nm。
14. according to the drilling fluid described in any one in claim 1-4,7-8 and 10-13, wherein, the titanium dioxide of the modification The preparation method of nano silicon particles includes：
(1) in the presence of monohydric alcohol and coupling agent, by shown in the one or more and formula (2) in the monomer of structure shown in formula (1) One or more in the monomer of structure carry out haptoreaction with nano SiO 2 particle；
(2) in the presence of redox initiation system, the catalytic product is subjected to polymerisation.
15. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, step (1) includes：First the monomer of structure shown in the monomer of structure shown in the formula (1) and formula (2) is mixed, and adjusted The pH to 7-9 of section gained mixture；Then again in the presence of monohydric alcohol and coupling agent, by the mixture and silica nanometer Grain carries out the haptoreaction.
16. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, the coupling agent is silane coupler.
17. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, the weight ratio of the nano SiO 2 particle and the dosage of the coupling agent is 100：0.2-10.
18. drilling fluid according to claim 17, wherein, the preparation method of the nano SiO 2 particle of the modification In, the weight ratio of the nano SiO 2 particle and the dosage of the coupling agent is 100：0.4-5.
19. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, the reducing agent in the redox initiation system is sodium hydrogensulfite, the oxidant in the redox initiation system For ammonium persulfate；The mol ratio of the reducing agent and oxidant is 1：1-5.
20. drilling fluid according to claim 19, wherein, the preparation method of the nano SiO 2 particle of the modification In, the mol ratio of the reducing agent and oxidant is 1：2.5-3.
21. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, relative to total dosage of the monomer of structure shown in the monomer of structure shown in 1mol formula (1) and formula (2), the redox The dosage of initiation system is 0.05-1g.
22. drilling fluid according to claim 21, wherein, the preparation method of the nano SiO 2 particle of the modification In, relative to total dosage of the monomer of structure shown in the monomer of structure shown in 1mol formula (1) and formula (2), the redox The dosage of initiation system is 0.07-0.8g.
23. drilling fluid according to claim 14, wherein, the preparation method of the nano SiO 2 particle of the modification In, the catalytic condition in step (1) includes：Temperature is 10-40 DEG C, time 10-60min；Polymerization in step (2) The condition of reaction includes：Temperature is 40-80 DEG C, time 3-6h.
24. according to the drilling fluid described in any one in claim 1-4, wherein, the bionical solid wall agent contains shown in formula (I) Construction unit：
In formula (I), R1For hydrogen,-CH2COOR3’、Or-CH2COOR3, R2For hydrogen,And R1And R2At least one of beN be more than 1 integer, n R5It is each independently group and n that H or described is derived from dopamine Individual R5At least one of for the group for being derived from dopamine, R4For H or C1-C10Alkyl, R " ' is H ,-CH2COOR3' or- CH2COOR3, and R1And R " ' it is different when be H, R3' it is hydrogen or alkali metal, R3For the group from dopamine.
25. drilling fluid according to claim 1, wherein, the preparation method of the bionical solid wall agent includes：
(1) polymer and formula that will contain the construction unit shown in formula (III) are R4CH=CHCOOH unsaturated carboxylic acid is carried out Graft copolymerization；
(2) polymer obtained by step (1) and dopamine and/or Dopamine hydrochloride are subjected to condensation reaction；
R ' and R " is each independently H or-CH2COOR3', and be H, R when R ' and R " is different3' it is hydrogen or alkali metal；R4For H or C1-C10Alkyl.
26. drilling fluid according to claim 25, wherein, in the preparation method of the bionical solid wall agent, in step (1) In, the condition of the graft copolymerization includes：Temperature is 50-90 DEG C, and the time is 1-10 hours；Containing shown in formula (III) The dosage and the mol ratio of the dosage of unsaturated carboxylic acid that the polymer of construction unit is counted using hydroxyl is 1：0.1-4.
27. drilling fluid according to claim 25, wherein, in the preparation method of the bionical solid wall agent, in step (2) In, the condition of the condensation reaction includes：Temperature is 10-50 DEG C, and the time is 2-48 hours；Polymer obtained by step (1) The mol ratio for total dosage that the dosage counted using carboxyl is counted with dopamine and Dopamine hydrochloride using amido is 1：0.01-0.2.
28. according to the drilling fluid described in any one in claim 1-4, wherein, the bionical shale control agent passes through following Method is prepared：In the presence of inorganic acid catalyst, arginine and lysine are subjected to condensation reaction, the arginic use Amount and the dosage mol ratio of lysine are 0.2-6：1, the weight that the condensation reaction condition makes obtained bionical shale control agent is equal Molecular weight is 800-4000g/mol.
29. drilling fluid according to claim 28, wherein, in the preparation method of the bionical shale control agent, the contracting Closing the condition of reaction includes：Temperature is 180-230 DEG C, time 4-20h.
30. drilling fluid according to claim 28, wherein, in the preparation method of the bionical shale control agent, the nothing The dosage of machine acid catalyst is 1 with the mol ratio of arginine and total dosage of lysine：0.3-3.
31. drilling fluid according to claim 28, wherein, in the preparation method of the bionical shale control agent, the nothing Machine acid catalyst is at least one of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid.
32. drilling fluid according to claim 1, wherein, it by weight ratio is 1 that the filler, which is,：1-2：1-2 1900- The calcium carbonate composition of 2200 mesh, 1000-1240 mesh and 720-920 mesh.
33. according to the drilling fluid described in any one in claim 1-4,7-8,10-13,15-23,25-27 and 29-32, its In, relative to the water in the drilling fluid of 100 parts by weight, the nanometer sealing agent, bionical solid wall agent and bionical shale suppress The total content of agent is below 10 parts by weight.
34. drilling fluid according to claim 33, wherein, it is described relative to the water in the drilling fluid of 100 parts by weight The content of filler is 1-5 parts by weight.
35. drilling fluid according to claim 1, wherein, the density of the drilling fluid is 2.3g/cm3More than.
36. drilling fluid according to claim 16, wherein, the coupling agent be gamma-aminopropyl-triethoxy-silane, γ- Glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane and N- (β-aminoethyl)- One or more in γ-aminopropyltrimethoxysilane.
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CN104946216B (en) * 2015-05-14 2016-05-18 中国石油大学(北京) A kind of bionical drilling fluid and preparation method thereof

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