CN110257025A - Water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive and preparation method thereof and water-base drilling fluid and application - Google Patents
Water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive and preparation method thereof and water-base drilling fluid and application Download PDFInfo
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- CN110257025A CN110257025A CN201910596309.4A CN201910596309A CN110257025A CN 110257025 A CN110257025 A CN 110257025A CN 201910596309 A CN201910596309 A CN 201910596309A CN 110257025 A CN110257025 A CN 110257025A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- 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
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/20—Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
- C09K8/206—Derivatives of other natural products, e.g. cellulose, starch, sugars
Abstract
The invention belongs to petroleum works field of oilfield chemistry, a kind of water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive and preparation method thereof and water-base drilling fluid and application are disclosed.The superhigh temperature fluid loss additive be after the crosslinked reaction of beta-cyclodextrin obtained product be added dropwise to containing oil phase with reacted in the continuous phase of emulsifier；It is white microballoon, and partial size is 20-75 μm, and swelling ratio is >=150%, temperature resistance ability >=180 DEG C.The present invention can effectively block nearly borehole wall micropore by the way that cyclodextrin microsphere is added into drilling fluid, reduce filter loss, and relatively small to the rheology impact of drilling fluid, and also can significantly reduce the filter loss of drilling fluid after high temperature ageing.Meanwhile the raw material for preparing cyclodextrin microsphere is renewable, environmentally protective, preparation process is simple, shows wide application prospect in environmental protection high performance water-based drilling fluid resistant to high temperatures.
Description
Technical field
The invention belongs to petroleum works field of oilfield chemistry, and in particular to a kind of water-base drilling fluid cyclodextrin microsphere superelevation
Temperature drop fluid loss agents and preparation method thereof and water-base drilling fluid and application.
Background technique
In recent years, as petrol resources exploitation is gradually expanded to the fields such as the deep ground of deep layer, unconventional, deep-well, ultradeep well etc.
The quantity of Holes of Complicated Wells gradually increases.With the increase of well depth, formation temperature rises, drilling well fluidity under high temperature and ultra-high temperature condition
The stabilization of energy, which has become, restricts one of deep formation oil-gas exploration and the technical bottleneck of exploitation.Wherein, it is bored under high-temperature and high-pressure conditions
If the leak-off wave making machine control of well liquid is improper, often cause a series of complex things such as bit freezing, borehole well instability, high frictional resistance and torque
Therefore.Therefore, the leak-off regulation in deep & ultra-deep well drilling process is one of key performance of drilling fluid.
Most important inorganic agent one of of the fluid loss additive as water-base drilling fluid plays the safe, fast, efficient drilling well of guarantee
Important function.Its dosage is larger, many kinds of.Different drop filters has been developed for Different Strata temperature drilling well demand at present
Agent type is lost, natural material or natural material modified product and synthesized polymer species are broadly divided into.Natural material or natural material
Modified product includes humic acid, cellulose, lignin, starch and its derivative；Synthetic polymer is mainly various vinyl
Monomeric polycarboxylic copolymer and sulfomethylated phenolic resin.Starch and cellulose derivative class fluid loss additive heatproof are lower than 150 DEG C,
The temperature resistant capability of resinae fluid loss additive is slightly strong, but also below 180 DEG C, and contamination resistance is limited.Therefore, it is applied to probing well
Bottom temperature be more than 180 DEG C of water-base drilling fluid fluid loss additive be mainly artificial synthesized AMPS multiple copolymer (by acrylonitrile AN,
2- acrylamide-2-methylpro panesulfonic acid AMPS and N, N '-dimethyl acrylamide DMAM polymerize) (Xia little Chun, easily
Bravely, Guo Lei waits the synthesis and performance study [J] Speciality Petrochemicals progress of drilling fluid high temperature resistant fluid loss additive FRT-2,
2012,13 (3): 7-9.), but artificial copolymer bio-toxicity and biological degradability are poor, and in the polymer synthesized often
Can also environment be impacted by also remaining a little monomer.
Therefore, the fluid loss additive resistant to high temperatures for developing environment-friendly type becomes the difficult point studied at present and emphasis.
Summary of the invention
The purpose of the invention is to overcome the drop of natural material or natural material modified product class of the existing technology
There is the defect of toxicity not environmentally to ask for defect of the fluid loss agents heatproof lower than 150 DEG C and artificial-synthetic copolymer's class fluid loss additive
Topic provides a kind of water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive and preparation method thereof and water-base drilling fluid and answers
With the present invention can not only significantly reduce high temperature superhigh temperature using cyclodextrin microsphere as water-base drilling fluid superhigh temperature fluid loss additive
Under the conditions of drilling fluid filter loss, keep the leak-off mud cake of Bao Erren, while the rheological characteristic variation of drilling fluid is less, in addition, this
Invention is using the degradable cyclodextrin of environmental protection as raw material, and not only temperature resistance ability is strong, but also environmental protection.
To achieve the goals above, first aspect present invention provides a kind of water-base drilling fluid cyclodextrin microsphere superhigh temperature
Fluid loss additive, wherein, will gelatinization treated beta-cyclodextrin under the conditions of the superhigh temperature fluid loss additive is existing for the crosslinking agent
The product obtained after crosslinked reaction be added dropwise to containing it is oily mutually with reacted in the continuous phase of emulsifier；Wherein, institute
Superhigh temperature fluid loss additive is stated as white microballoon, average grain diameter is 20-75 μm, and water absorption and swelling rate is >=150%, temperature resistance ability >=
180℃。
Second aspect of the present invention provides a kind of aforementioned water-base drilling fluid cyclodextrin microsphere superhigh temperature filtrate reducing
The preparation method of agent, wherein method includes the following steps:
(1) beta-cyclodextrin is carried out gelatinization with alkaline solution to react, then the beta-cyclodextrin after gelatinization is carried out with crosslinking agent
Cross-linking reaction obtains dispersed phase；
(2) continuous phase mutually is obtained with emulsifier progress emulsion reaction by oily；
(3) dispersed phase is added dropwise to progress inverse emulsion polymerization reaction in the continuous phase；
(4) product that step (3) obtains is washed and is dried.
Third aspect present invention provides a kind of water-base drilling fluid, wherein the water-base drilling fluid contains aforementioned described
Water-base drilling fluid made from water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive or the aforementioned preparation method is used
Cyclodextrin microsphere superhigh temperature fluid loss additive.
Fourth aspect present invention provides application of the aforementioned water-base drilling fluid of one kind in probing high temperature well.
Through the above technical solutions, compared with prior art, the invention has the following beneficial effects:
(1) cyclodextrin microsphere prepared by the present invention can significantly reduce the superhigh temperature leak-off of water-base drilling fluid at low concentrations
Amount, forms the mud cake of Bao Erren, compared with conventional polymerization species fluid loss additive, reduces the leak-off under high temperature ultra-high temperature condition
Ability increases substantially.
(2) conventional polymerization species fluid loss additive is added in drilling fluid, can cause the significant raising of drilling fluid viscosity, and
Cyclodextrin microsphere prepared by the present invention is smaller to the viscosity influence of drilling fluid, is conducive to the pumping of drilling fluid.
(3) raw material of cyclodextrin microsphere prepared by the present invention is biomass, from a wealth of sources, environmental-friendly, and prepares work
Skill is simple.During preparing cyclodextrin microsphere using reversed emulsion polymerization, absolutely not introduces any noxious material and participate in
Reaction, guaranteeing entire reaction process all is asepsis environment-protecting that is environmentally protective, therefore also ensuring product particles.Also, this hair
The preparation condition of the cyclodextrin microsphere of bright preparation is simple, and technological operation is easy, convenient for large-scale industrial production and application.
Detailed description of the invention
Fig. 1 is the thermogravimetric curve contrast curve chart of cyclodextrin microsphere prepared by embodiment 1 and beta-cyclodextrin；
Fig. 2 is that the cyclodextrin microsphere of the preparation of embodiment 1 and the filtrate loss controllability of conventional superhigh temperature fluid loss additive compare and illustrate
Figure.
Description of symbols
1 cyclodextrin microsphere, 2 beta-cyclodextrin, 3 base starches 4 base slurry+1%SPNH
5 base slurry+1%Soltex, 6 base slurry+1%Asphasol Supreme
7 bases starch the cyclodextrin microsphere of+1% embodiment 1 preparation
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive, wherein institute
Under the conditions of to state superhigh temperature fluid loss additive be existing for the crosslinking agent, it will be obtained after gelatinization treated the crosslinked reaction of beta-cyclodextrin
Product be added dropwise to containing it is oily mutually with reacted in the continuous phase of emulsifier；Wherein, the superhigh temperature fluid loss additive
For white microballoon, average grain diameter is 20-75 μm, and water absorption and swelling rate is >=150%, temperature resistance ability >=180 DEG C.
It according to the present invention, is aforementioned by the average grain diameter of the cyclodextrin microsphere, water absorption and swelling degree and temperature resistance capability control
Within the scope of, the superhigh temperature fluid loss additive being prepared can be made to can reduce leak-off of the water-base drilling fluid under ultra-high temperature condition
Amount.
In the case of, according to the invention it is preferred to, the average grain diameter of the superhigh temperature fluid loss additive is 30-75 μm, water absorption and swelling
Rate is >=300%, and temperature resistance ability is 180-200 DEG C, and in more preferable situation, temperature resistance ability is up to 200 DEG C, in the present invention, benefit
The cyclodextrin for using environmental protection degradable is as raw material, and by temperature resistance capability improving to 200 DEG C, not only temperature resistance ability is strong, but also ring
It protects.
Can make the superhigh temperature fluid loss additive being prepared preferably reduces filter of the water-base drilling fluid under ultra-high temperature condition
Vector.Wherein, swellbility can reflect the size of its water absorbing capacity and the intensity of water suction front and back to a certain extent.
According to the present invention, cyclodextrin (CD) is amylose in the cyclodextrin glycosyltransferase generated by bacillus
A series of general name of the lower cyclic oligosaccharides generated of effect, is a kind of native compound from a wealth of sources, cyclodextrin point surface contains
There is brothers hydroxyl abundant, easily it is chemically crosslinked and is modified, widens its application range.It is most common to have α-CD, β-CD
With γ-CD, wherein α-CD molecule cavity inside diameter is smaller, is typically only capable to inclusion compared with small molecule guest species, application range is smaller；
γ-CD high production cost, cannot a large amount of industrial productions, using being restricted.β-CD is to pass through α-by 7 D- glucopyranoses
Cyclic oligosaccharide made of Isosorbide-5-Nitrae glucosides key joint, and it is nontoxic be easy to get, have hydrophilic appearance and hydrophobic inner cavity, usually
As host molecule super-molecule assembling body can be formed with guest molecule.
The present inventor passes through a large amount of scientific experiment, has been surprisingly found that: the cyclodextrin of the crosslinked preparation of beta-cyclodextrin
Microballoon had not only remained the original cavity structure of beta-cyclodextrin, but also has enhanced the hydrophobicity in beta-cyclodextrin hole.In high temperature action
Under, the fine particle that cyclodextrin microsphere by the hydrophilic radicals adsorbed water molecule such as hydroxyl, can become expansiveness participates in shape
At mud cake, deformable filler improves the consistency of mud cake in the gap of mud cake, and filter loss is effectively reduced.Simultaneously as its
A large amount of hydrophilic functional groups are contained on surface, and cyclodextrin microsphere can also be made by the functional groups such as the hydroxyl on surface and clay particle
With, and then certain grid structure is formed, play the role of reducing filter loss.In addition, the water suction of cyclodextrin microsphere at high temperature
Swelling ratio is far longer than the water absorption and swelling rate under room temperature, and hydrone is attracted to the surface of cyclodextrin microsphere, and result is equivalent to
The reduction of free water content in system, this has also played the effect of filtrate reducing to a certain extent.Cyclodextrin microsphere is used at present
It is had not been reported in the research of the leak-off of regulation drilling fluid.
According to the present invention, in the superhigh temperature fluid loss additive beta-cyclodextrin content >=60 weight %, preferably 60-75 weight
Measure %, more preferably 65-73 weight %；In the present invention, in the superhigh temperature fluid loss additive content of beta-cyclodextrin be for
Characterize the content of beta-cyclodextrin in the fluid loss additive of synthesis.Because fluid loss additive is handed over by beta-cyclodextrin and epoxychloropropane etc.
Made of joining agent reaction, the dosage of reaction can be participated in by beta-cyclodextrin in final product that detection method detects.This
The inventor of invention has found that the content control by beta-cyclodextrin in the superhigh temperature fluid loss additive is by a large amount of scientific experiment
Within above range, it can make the superhigh temperature fluid loss additive being prepared that can significantly reduce water-base drilling fluid under ultra-high temperature condition
Filter loss；If the content of beta-cyclodextrin is lower than 60 weight %, for example, when 40 weight %, then in high temperature ultra-high temperature condition
Under filtrate reducing significant effect weaken.
Second aspect of the present invention provides a kind of aforementioned water-base drilling fluid cyclodextrin microsphere superhigh temperature filtrate reducing
The preparation method of agent, wherein method includes the following steps:
(1) beta-cyclodextrin is carried out gelatinization with alkaline solution to react, then the beta-cyclodextrin after gelatinization is carried out with crosslinking agent
Cross-linking reaction obtains dispersed phase；
(2) continuous phase mutually is obtained with emulsifier progress emulsion reaction by oily；
(3) dispersed phase is added dropwise to progress inverse emulsion polymerization reaction in the continuous phase；
(4) product that step (3) obtains is washed and is dried.
According to the present invention, in step (1), beta-cyclodextrin is subjected to gelatinization with alkaline solution and is reacted, wherein the gelatinization
The condition of reaction includes: that temperature can be 30-40 DEG C, and the time can be 25-60min.In the present invention, add alkali purpose be by
Beta-cyclodextrin gelatinization.
According to the present invention, the alkaline solution can be alkali soluble solution obtained in the deionized water, wherein the alkali can be with
For one of sodium hydroxide, potassium hydroxide and barium hydroxide or a variety of, preferably sodium hydroxide, the mass fraction of the alkali are
20-40%.
According to the present invention, beta-cyclodextrin can be commercially available, for example, can be limited purchased from Chinese medicines group chemical reagent
Company, in addition, the quality volume fraction of the beta-cyclodextrin is 30-65%.
According to the present invention, the condition of the cross-linking reaction, which includes: temperature, to be 25-40 DEG C, and the time can be 1-3h；It is excellent
In the case of choosing, temperature is 30-35 DEG C, time 1.5-3h.
According to the present invention, the crosslinking agent is in epoxychloropropane, sodium trimetaphosphate, phosphorus oxychloride and calgon
It is one or more, preferably epoxychloropropane or sodium trimetaphosphate；In addition, in the present invention, when the crosslinking agent is epoxy chlorine
When propane, under preferable case, the crosslinking agent epoxychloropropane is dripped to by the way of being added dropwise by alkali, deionized water and β-CD
In solution, wherein drop rate can be 10-40g/20min, preferably 15-30g/20min.In the present invention, it needs to illustrate
, when using crosslinking agent such as sodium trimetaphosphate, phosphorus oxychloride and calgon, due to sodium trimetaphosphate, phosphorus oxychloride
All it is solid with calgon, then does not have to limit drop rate.
According to the present invention, the weight ratio of the dosage of the beta-cyclodextrin and the crosslinking agent can be 1:(1-20), preferably
For 1:(1.2-5).
According to the present invention, relative to the deionized water of 100mL, the dosage of the alkali is 20-40g, the beta-cyclodextrin
Dosage is 30-65g.
According to the present invention, in step (2), the oil can be mutually vegetable oil, kerosene, atoleine, n-butanol, chlorine
One of imitative, toluene and methylene chloride are a variety of, preferably one of kerosene, chloroform, atoleine and toluene or a variety of.
According to the present invention, the emulsifier is compound emulsifying agent, and in the present invention, the emulsifier can be (main for Span
Wanting ingredient is sorbitan fatty ester) serial emulsifier and Tween (polyoxyethylene sorbitan monolaurate and
The mixture of the double Span 20s of a part of polyoxyethylene) serial emulsifier compounding, alternatively, the emulsifier
It can compounding for Span series emulsifier and OP (polyethenoxy alkylphenols) series emulsifier；Wherein, Span series cream
The mass ratio of agent and Tween series emulsifier is (4-10): 1；The mass ratio of Span series emulsifier and OP series emulsifier
For (3-10): 1.
According to the present invention, relative to the oily phase of 100mL, the dosage of the emulsifier (compound emulsifying agent) is 0.3-
1g, preferably 0.3-0.8g.
According to the present invention, the condition of the emulsion reaction includes: that emulsifying temperature can be for 50-80 DEG C, and emulsification times can be with
For 3-24h；Under preferable case, temperature is 55-70 DEG C, time 3-12h.
According to the present invention, in step (3), the volume ratio of the dosage of the dispersed phase and the continuous phase can be 1:
(2-6), preferably 1:(2-4).
According to the present invention, in step (3), the dispersed phase is added dropwise in the continuous phase and is reacted, wherein institute
The rate for stating dropwise addition can be 10-40g/20min.
According to the present invention, in step (4), it is described washing for successively dilute HCl solution, dehydrated alcohol, deionized water and
It is washed in acetone soln；Wherein, the number of washing and dilute HCl solution, dehydrated alcohol, deionized water and acetone soln
Dosage is not particularly limited, under preferable case, using multiple washing.
According to the present invention, in step (4), the temperature of the drying can be 40-75 DEG C.
In the case of, according to the invention it is preferred to, this method carries out under agitation, wherein mixing speed can be 600-
2000rpm, in addition, mixing time can be 5-12h.
Third aspect present invention provides a kind of water-base drilling fluid, wherein the water-base drilling fluid contains aforementioned described
Water-base drilling fluid made from water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive or the aforementioned preparation method is used
Cyclodextrin microsphere superhigh temperature fluid loss additive.
According to the present invention, relative to the water-base drilling fluid of 100mL, the dosage of the cyclodextrin microsphere superhigh temperature fluid loss additive
For 0.1-5g, preferably 0.3-3g.
According to the present invention, the water-base drilling fluid can also include other inorganic agents, and under preferable case, the inorganic agent can
To select drilling fluid to use with puddled soil, high temperature anti-sloughing agent, high-temperature lubricant, high temperature polymer coating agent, high temperature sulfonation class filtrate reducing
One of agent, high-temperature viscosity reducer, high-temperature stabilizer and heavy weight additive are a variety of.
Wherein, it can be temperature resistance bentonite commonly used in the art, preferably concave convex rod that the drilling fluid, which is used with puddled soil,
Soil, effect are the viscosity and shear force increased under drilling fluids at high temperature, reduce the filter loss of drilling fluid.
Wherein, the anti-sloughing agent that the high temperature anti-sloughing agent can be usually applicable for this field, preferably sulfonated gilsonite, high softening
At least one of point bitumen, emulsified asphalt.
Wherein, the high-temperature lubricant can be high-temperature lubricant commonly used in the art, preferably hypotoxicity mineral
At least one of oil, elastic graphite, modified vegetable oil.
Wherein, the high temperature polymer coating agent can be coating agent commonly used in the art, preferably amphoteric ion
At least one of polymer FA367, polyacrylic acid potassium, co-polymer of sulfonate, acrylamide copolymer.
Wherein, the high temperature sulfonation class fluid loss additive is sulfonated-pheno-formoldehyde resin, in sulfonated lignite, sulfonated lignite resin
It is at least one.
Wherein, the high-temperature viscosity reducer can be thinner commonly used in the art, the preferably sulfomethylated lignin of Chrome-free
At least one of hydrochlorate, Sodium Polyacrylate, fluosilicic thinner SF-260, Sulfonated Copolymer of Styrene and Maleic Anhydride.
Wherein, the high-temperature stabilizer is at least one of sulfurous acid acid sodium, thiocarbamide and D-araboascorbic acid sodium.
Wherein, the heavy weight additive can be heavy weight additive commonly used in the art, preferably barite, Iron Ore Powder, four oxygen
Change at least one of three manganese, calcium carbonate, potassium formate and sodium formate.
In the present invention, relative to the water-base drilling fluid of 100 parts by weight, the content with puddled soil is 1-4 parts by weight, institute
The content for stating high temperature anti-sloughing agent is 1-7 parts by weight, and the content of the high-temperature lubricant is 2-10 parts, the high temperature polymer coating
The content of agent is 0.1-0.5 parts by weight, and the content of the high temperature sulfonation class fluid loss additive is 3-10 parts by weight, the high temperature viscosity reduction
The content of agent is 1-2 parts by weight, and the content of the high-temperature stabilizer is 0.5-2 parts by weight, and the content of the heavy weight additive is according to brill
The density of well liquid is adjusted.
Fourth aspect present invention provides application of the aforementioned water-base drilling fluid of one kind in probing high temperature well.
According to the present invention, the temperature of the high temperature well can be 180-200 DEG C.
The present invention will be described in detail by way of examples below.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as nothing
Specified otherwise can obtain from commercial channels.
1, the test method of swelling ratio and steps are as follows: the β-CD microballoon of 5 parts of different qualities is accurately weighed, at room temperature in water
For 24 hours, supernatant liquor is removed in 3000r/min centrifugation 20min hypsokinesis for middle immersion, and accurate title after the free water of microsphere surface is absorbed with filter paper
Weight, calculates its swelling ratio.
Swelling ratio (SR) can be calculated according to the following formula:
SR=(W1-W0)/W0× 100%
Wherein, W0For the quality for being swollen preceding microballoon, W1For the quality of microballoon after swelling.
2, using the content of beta-cyclodextrin in colorimetric method for determining beta-cyclodextrin microballoon.
The basic principle of colorimetric method is that beta-cyclodextrin is hydrolyzed into glucose in 0.5mol/L sulfuric acid solution first, then
Utilize content (preparation, structural characterization and its Release Performance of poly- beta-cyclodextrin sustained-release micro-spheres of spectrophotometer detection glucose
Research).
Its specific method is:
(1) preparation of glucose standard curve
Dry DEXTROSE ANHYDROUS 60mg is weighed, appropriate distilled water is added and dissolves and is settled to 100mL.Take above-mentioned reference substance
Solution 1.0,1.5,2.0,2.5,3.0mL, are settled to 50mL.Each 2mL of above-mentioned solution is taken, 4% phenol solution 1mL is separately added into,
It mixes, is rapidly added the 7.0mL concentrated sulfuric acid, shakes up, keep the temperature 30min in 40 DEG C of water-baths, take out, 5min is placed in ice bath, is taken
Out.It is ibid operated with 2.0mL distilled water as blank, after full wavelength scanner to maximum absorption wavelength, measures trap.Calculate grape
Standard curve of the sugared concentration to trap.
(2) in beta-cyclodextrin microballoon beta-cyclodextrin content
It weighs beta-cyclodextrin microballoon 25mg to be measured to be placed in test tube, the sulfuric acid 15mL of 0.5mol/L is added, in 100 DEG C of oil baths
Middle reaction 8h.Then hydrolyzate is transferred in 50mL volumetric flask, cleans hydrolysate to transfer with the sulfuric acid solution of 0.5mol/L
Completely, finally, taking 5% phenol solution 0.75mL respectively with pipette, concentrated sulfuric acid 4.5mL, hydrolyzate 1.25mL mixing are carried out
Chromogenic reaction, and absorption angle value of the glucose measured according to ultraviolet-uisible spectrophotometer at 490nm, in cyclodextrin microsphere
The content of beta-cyclodextrin is calculated according to the following formula:
Wherein, Cglucose is the concentration of glucose that ultraviolet-uisible spectrophotometer measures, and V is miscible solution volume, and W is
The quality of cyclodextrin microsphere.
3, micro- using Bettersize2000 laser particle size analyzer (Dandong Bai Te Instrument Ltd.) test cyclodextrin
The particle diameter distribution of ball, test method are as follows: cyclodextrin microsphere is added to be configured in dehydrated alcohol 0.1% suspension, ultrasound
It is tested immediately after dispersion 10min.
Embodiment 1
The present embodiment indicates that the cyclodextrin microsphere prepared using method of the invention.
(1) in the case where temperature is 30 DEG C, 16g NaOH is added in 64mL deionized water, 24g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 40min, wherein control mixing speed is 800rpm；Then, it is slowly added dropwise
29.5g epoxychloropropane, 20min are dripped off, and holding temperature is 30 DEG C of reaction 1.5h, obtain dispersed phase.
(2) 0.8g Span-80 and 0.2g Tween-20 is added in 160mL kerosene, under conditions of temperature is 70 DEG C
It makes it dissolve or disperses after stirring 10min, emulsify 3h, obtain continuous phase.
(3) dispersed phase (cyclodextrin solution of cross-linking reaction) is slowly dropped to continuous phase (kerosene and emulsifier progress cream
Change the product that reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:4, and drop rate is
40g/20min, after being added dropwise by rotational speed regulation be 2000rpm, while be warming up to 70 DEG C and maintain temperature stablize reaction 6h.
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 60 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-1 (Cyclodextrin Microsphere-1).
Average grain diameter, the water absorption and swelling rate of the cyclodextrin microsphere are as shown in table 1.
In addition, Fig. 1 is the thermogravimetric curve correlation curve of cyclodextrin microsphere prepared by the embodiment of the present invention 1 and beta-cyclodextrin
Figure, wherein what curve 1 indicated is the thermogravimetric curve of cyclodextrin microsphere, and what curve 2 indicated is the thermogravimetric curve of beta-cyclodextrin, from
Fig. 1, which can be seen that cyclodextrin microsphere and be more than 290 DEG C or so in temperature, just takes place apparent weightlessness, shows it with excellent
Thermal stability, can be applied in high temperature and ultra-high temperature drilling liquid.
Embodiment 2
The present embodiment indicates that the cyclodextrin microsphere prepared using method of the invention.
(1) in the case where temperature is 30 DEG C, 10g NaOH is added in 40mL deionized water, 12g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 25min, wherein control mixing speed is 800rpm；Then, it is slowly added dropwise
17.6g epoxychloropropane, 20min are dripped off, and holding temperature is 30 DEG C of reaction 1.5h, obtain dispersed phase.
(2) 0.6g Span-60 and 0.2g OP-10 is added in 80mL chloroform, is stirred under conditions of temperature is 55 DEG C
It makes it dissolve or disperses after 20min, emulsify 12h, obtain continuous phase.
(3) dispersed phase (cyclodextrin solution of cross-linking reaction) is slowly dropped to continuous phase (chloroform and emulsifier progress cream
Change the product that reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:2, and drop rate is
30g/20min, after being added dropwise by rotational speed regulation be 1200rpm, while be warming up to 70 DEG C and maintain temperature stablize reaction 5h.
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 60 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-2 (Cyclodextrin Microsphere-2).
Average grain diameter, the water absorption and swelling rate of the cyclodextrin microsphere are as shown in table 1.
Embodiment 3
The present embodiment indicates that the cyclodextrin microsphere prepared using method of the invention.
(1) in the case where temperature is 40 DEG C, 16g NaOH is added in 40mL deionized water, 26g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 60min, wherein control mixing speed is then 800rpm adds 35.1g
Sodium trimetaphosphate, holding temperature are 40 DEG C of reaction 3h, obtain dispersed phase.
(2) 0.53g Span-80 and 0.13g Tween-60 is added in 120mL atoleine, is 80 DEG C in temperature
Under the conditions of stir 30min after make it dissolve or disperse, emulsify 3h, obtain continuous phase.
(3) by dispersed phase (cyclodextrin solution of cross-linking reaction) be slowly dropped to continuous phase (atoleine and emulsifier into
The product that row emulsion reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:6, and speed is added dropwise
Rate is 20g/20min, after being added dropwise by rotational speed regulation be 1000rpm, while be warming up to 50 DEG C and maintain temperature stablize reaction
12h。
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 75 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-3 (Cyclodextrin Microsphere-3).
Average grain diameter, the water absorption and swelling rate of the cyclodextrin microsphere are as shown in table 1.
Embodiment 4
The present embodiment indicates that the cyclodextrin microsphere prepared using method of the invention.
(1) in the case where temperature is 30 DEG C, 16g NaOH is added in 40mL deionized water, 12g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 30min, wherein control mixing speed is then 800rpm adds 15.2g
Sodium trimetaphosphate, holding temperature are 30 DEG C of reaction 2h, obtain dispersed phase.
(2) 1.92g Span-60 and 0.48g Tween-20 is added in 240mL toluene, the condition for being 80 DEG C in temperature
It makes it dissolve or disperses after lower stirring 20min, emulsification for 24 hours, obtains continuous phase.
(3) dispersed phase (cyclodextrin of cross-linking reaction is molten) liquid is slowly dropped to continuous phase (toluene and emulsifier progress cream
Change the product that reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:3, and drop rate is
10g/20min, after being added dropwise by rotational speed regulation be 600rpm, while be warming up to 80 DEG C and maintain temperature stablize reaction 5h.
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 40 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-4 (Cyclodextrin Microsphere-4).
Average grain diameter, the water absorption and swelling rate of the cyclodextrin microsphere are as shown in table 1.
Embodiment 5
(1) in the case where temperature is 25 DEG C, 15g NaOH is added in 60mL deionized water, 30g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 60min, wherein control mixing speed is 1500rpm；Then, it is slowly added to 80g
Calgon, 20min are dripped off, and holding temperature is 25 DEG C of reaction 3h, obtain dispersed phase.
(2) 1.2g Span-80 and 0.25g Tween-60 is added in 180mL kerosene, under conditions of temperature is 60 DEG C
It makes it dissolve or disperses after stirring 10min, emulsify 8h, obtain continuous phase.
(3) dispersed phase (cyclodextrin solution of cross-linking reaction) is slowly dropped to continuous phase (kerosene and emulsifier progress cream
Change the product that reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:4, and drop rate is
25g/20min, after being added dropwise by rotational speed regulation be 1500rpm, while be warming up to 60 DEG C and maintain temperature stablize reaction 6h.
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 60 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-5 (Cyclodextrin Microsphere-5).
Embodiment 6
(1) in the case where temperature is 30 DEG C, 20g NaOH is added in 60mL deionized water, 32g β-CD is added after stirring and dissolving,
Dissolution obtains the solution of homogeneous transparent after stirring 50min, wherein control mixing speed is 800rpm；Then, it is slowly added to
39.8g phosphorus oxychloride, 20min are dripped off, and holding temperature is 30 DEG C of reaction 2h, obtain dispersed phase.
(2) 1.5g Span-80 and 0.15g OP-10 is added in 180mL kerosene, is stirred under conditions of temperature is 65 DEG C
It makes it dissolve or disperses after mixing 10min, emulsify 10h, obtain continuous phase.
(3) dispersed phase (cyclodextrin solution of cross-linking reaction) is slowly dropped to continuous phase (kerosene and emulsifier progress cream
Change the product that reaction obtains) in, wherein the volume ratio of the dosage of the dispersed phase and the continuous phase is 1:4, and drop rate is
35g/20min, after being added dropwise by rotational speed regulation be 1800rpm, while be warming up to 65 DEG C and maintain temperature stablize reaction 6h.
(4) after reaction, product is successively sufficiently washed with dilute hydrochloric acid, dehydrated alcohol, distilled water, acetone, at 60 DEG C
Vacuum drying obtains product.
It is denoted as CDMS-6 (Cyclodextrin Microsphere-6).
Comparative example 1
Using sulfonated lignite resin (SPNH) fluid loss additive, it is denoted as DS1.
Comparative example 2
Using sulfonated gilsonite (Soltex) fluid loss additive, it is denoted as DS2.
Comparative example 3
Using modified pitch (Asphasol Supreme) fluid loss additive, it is denoted as DS3.
Comparative example 4
Prepare cyclodextrin microsphere in the same manner as shown in Example 1, the difference is that: be added β-CD amount be
6.4g。
It is denoted as DS4, average grain diameter, water absorption and swelling rate, total pore size volume and the temperature resistance ability of the fluid loss additive such as 1 institute of table
Show.
Comparative example 5
Prepare cyclodextrin microsphere in the same manner as shown in Example 1, institute the difference is that: dispersion is added to continuous
Mixing speed after phase is 400rpm.
It is denoted as DS5, average grain diameter, water absorption and swelling rate, total pore size volume and the temperature resistance ability of the fluid loss additive such as 1 institute of table
Show.
Table 1
| Sample | Partial size/μm | Water absorption and swelling rate/% | The content of beta-cyclodextrin in cyclodextrin microsphere |
| CDMS-1 | 25.4 | 480 | 71.2 |
| CDMS-2 | 35.6 | 350 | 65.6 |
| CDMS-3 | 46.8 | 325 | 64.0 |
| CDMS-4 | 74.5 | 312 | 72.5 |
| CDMS-5 | 32.4 | 445 | 65.8 |
| CDMS-6 | 28.7 | 467 | 60.2 |
| DS4 | 46.3 | 150 | 52.6 |
| DS5 | 123.2 | 80 | 64.4 |
It can be seen that the cyclodextrin microsphere prepared using method of the invention by the result of table 1, for example,
Embodiment 1-6, the cyclodextrin microsphere have biggish water absorption and swelling rate, advantageously reduce filter loss.
Test case
The preparation of bentonite base slurry: 16g drilling fluid sodium bentonite (magnificent Weihe River bentonite is added in 400mL tap water
Co., Ltd), 10000r/min stirring 30min after it is closed stand obtain for 24 hours prehydration 4% bentonite base slurry.
It is separately added into 4g fluid loss additive sample in the bentonite base slurry of above-mentioned preparation, after 10000r/min stirs 20min
Slurries are put into ageing can, ageing can is placed in high temp roller heating furnace, and the heat rolling 16h at 200 DEG C, wait starch after heat rolling
Liquid is cooled to room temperature, and 10000r/min stirs 10min and tests size performance.In addition, inorganic agent sample is embodiment 1-6 and right
The fluid loss additive prepared in ratio 1-5.
According to the test method of GB/T16783.2-2012, various kinds obtained is tested using the fast rotational viscometer of ZNN-D6 six
600 turns, 300 turns, 200 turns, 100 turns, 6 turns and 3 turns of reading of product, then calculate apparent viscosity (AV), plastic viscosity (PV),
Yield value (YP) and API filtration (FLAPI), test result is as shown in table 2 and table 3.
Sulfonated lignite resin fluid loss additive (SPNH) used takes limited liability company for CNOOC and provides, sulfonated gilsonite
Soltex provides for Chevron Corporation (Stardard Oil Company of California), and modified pitch Asphasol Supreme is provided by Mike bar mud company.
Table 2 is influence of the different fluid loss additives to bentonite slurry rheological characteristic and leak-off.
Table 2
From 2 test result of table can be seen that 4% bentonite base starch 200 DEG C heat rolling 16h after API filtration be up to
51.8mL.It is starched in 4% bentonite base and 1% fluid loss additive is added, the filter loss after 200 DEG C of heat rolling 16h has different degrees of drop
Low, wherein preparation-obtained cyclodextrin microsphere filtrate reducing effect of the invention is the most prominent, API filtration is minimum, better than existing
High temperature fluid loss additive in technology, such as DS1, DS2 and DS3, also superior to the filtrate reducing not prepared using method of the invention
Agent DS4 and DS5 show excellent high temperature filtrate loss controllability.
High temperature aqueous-based drilling fluid composition is prepared, specific formula is as follows:
1# formula: 2% magnificent Weihe River drilling fluid sodium bentonite+0.5%NaOH+0.5%Na2SO3+ 1%Driscal-D+
3%SPNH+3% sulfonated phenolic resin SMP -2+2%GR-1+5% ultrafine calcium (300 mesh)+2%7# white oil+0.5%Span-80.
2# formula: 1# formula+2%CDMS-1
By above-mentioned 2 prepared drilling fluid compositions, heat rolls 16h at 200 DEG C, tests the rheological characteristic of drilling fluid after heat rolling
And API filtration.
The rheological characteristic and leak-off test result of 200 DEG C of heat rolling front and backs of the different drilling fluid compositions of table 3.
Table 3
It can be seen that compared with 1# formula from 3 test result of table, the cyclodextrin microsphere that embodiment 1 obtains be added to height
After in warm drilling fluid composition, the API filtration after 200 DEG C of heat rollings is significantly reduced, and shows excellent high temperature filtrate loss controllability.
In addition, Fig. 2 is the filtration reduction of cyclodextrin microsphere prepared by the embodiment of the present invention 1 and conventional superhigh temperature fluid loss additive
Energy contrast schematic diagram, wherein what 3 bar shaped columns represented is base slurry, and what 4 bar shaped columns represented is base slurry+1%SPNH, 5 bar shaped columns
That shape represents is base slurry+1%Soltex, and what 6 bar shaped columns represented is base slurry+1%Asphasol Supreme, 7 bar shaped columns
What is represented is the cyclodextrin microsphere that base starches the preparation of+1% embodiment 1, as can be seen from Figure 2: being made using containing the embodiment of the present invention 1
The API filtration of the water-base drilling fluid of standby cyclodextrin microsphere is low.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive, which is characterized in that the superhigh temperature fluid loss additive
Under the conditions of for existing for the crosslinking agent, by the product obtained after gelatinization treated the crosslinked reaction of beta-cyclodextrin be added dropwise to containing
It is oily mutually with reacted in the continuous phase of emulsifier；Wherein, the superhigh temperature fluid loss additive is white microballoon, average grain
Diameter is 20-75 μm, and water absorption and swelling rate is >=150%, temperature resistance ability >=180 DEG C.
2. superhigh temperature fluid loss additive according to claim 1, wherein the average grain diameter of the superhigh temperature fluid loss additive is
30-75 μm, water absorption and swelling rate is >=300%, 180-200 DEG C of temperature resistance ability.
3. superhigh temperature fluid loss additive according to claim 1 or 2, wherein beta-cyclodextrin in the superhigh temperature fluid loss additive
Content >=60 weight %, preferably 60-75 weight %.
4. the system of water-base drilling fluid cyclodextrin microsphere superhigh temperature fluid loss additive described in a kind of any one of claim 1-3
Preparation Method, which is characterized in that method includes the following steps:
(1) beta-cyclodextrin is carried out gelatinization with alkaline solution to react, then the beta-cyclodextrin after gelatinization is crosslinked with crosslinking agent
Reaction obtains dispersed phase；
(2) continuous phase mutually is obtained with emulsifier progress emulsion reaction by oily；
(3) dispersed phase is added dropwise to progress inverse emulsion polymerization reaction in the continuous phase；
(4) product that step (3) obtains is washed and is dried.
5. according to the method described in claim 4, wherein, in step (1), the condition of the gelatinization reaction includes: that temperature is
30-40 DEG C, time 25-60min；
Preferably, it is 25-40 DEG C that the condition of the cross-linking reaction, which includes: temperature, time 1-3h；
Preferably, the crosslinking agent is one of epoxychloropropane, sodium trimetaphosphate, phosphorus oxychloride and calgon or more
Kind；
Preferably, the alkaline solution be alkali be dissolved in obtained in deionized water, the alkali be sodium hydroxide, potassium hydroxide and
One of barium hydroxide is a variety of；
Preferably, the weight ratio of the dosage of the beta-cyclodextrin and the crosslinking agent is 1:(1-20), preferably 1:(1.2-5)；
Preferably, relative to the deionized water of 100mL, the dosage of the alkali is 20-40g, and the dosage of the beta-cyclodextrin is 30-
65g。
6. according to the method described in claim 4, wherein, in step (2), the oil is mutually vegetable oil, kerosene, liquid stone
One of wax, n-butanol, chloroform, toluene and methylene chloride are a variety of；
Preferably, the emulsifier be Span series emulsifier and Tween series emulsifier compound or the emulsification of Span series
Agent is compounded with OP series emulsifier；
Preferably, the mass ratio of Span series emulsifier and Tween series emulsifier is (4-10): 1；Span series emulsifier with
The mass ratio of OP series emulsifier is (3-10): 1；
Preferably, relative to the oily phase of 100mL, the dosage of the emulsifier is 0.3-1g；
Preferably, it is 50-80 DEG C that the condition of the emulsion reaction, which includes: temperature, time 3-24h.
7. according to the method described in claim 4, wherein, in step (3), the dosage of the dispersed phase and the continuous phase
Volume ratio is 1:(2-6)；
Preferably, the rate of the dropwise addition is 10-40g/20min.
8. according to the method described in claim 4, wherein, in step (4), the washing is successively in dilute hydrochloric acid solution, nothing
It is washed in water-ethanol, deionized water and acetone soln；
Preferably, the temperature of the drying is 40-75 DEG C.
9. the method according to any one of claim 4-8, wherein this method carries out under agitation, wherein stirs
Mixing speed is 600-2000rpm.
10. a kind of water-base drilling fluid, which is characterized in that the water-base drilling fluid contains described in any one of claim 1-3
Water-base drilling fluid preparation method described in any one of cyclodextrin microsphere superhigh temperature fluid loss additive or claim 4-9
Water-base drilling fluid obtained cyclodextrin microsphere superhigh temperature fluid loss additive.
11. water-base drilling fluid according to claim 10, wherein relative to the water-base drilling fluid of 100mL, the cyclodextrin
The dosage of microballoon superhigh temperature fluid loss additive is 0.1-5g, preferably 0.3-3g.
12. application of the water-base drilling fluid described in claim 10 or 11 in probing high temperature well.
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| CN114456317A (en) * | 2021-06-22 | 2022-05-10 | 中海油能源发展股份有限公司 | Modified cyclodextrin shale inhibitor for water-based drilling fluid and preparation method thereof |
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