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 application of carbosphere in high temperature aqueous-based drilling fluid sealing agent, and the carbon is micro-
The average grain diameter of ball is 50-50000nm, oxygen-containing functional group total amount >=0.2mmol/g.In the present invention, the high temperature aqueous-based brill
Well liquid is to refer to the water-base drilling fluid used in 200 DEG C of subsurface environment.
Preferably, the average grain diameter of the carbosphere is 50-3000nm, further preferably 200-1500nm.
Preferably, the oxygen-containing functional group total amount of the carbosphere is 0.20-0.31mmol/g.In the present invention, " oxygen-containing official
Total amount can be rolled into a ball " total content that refers to carbosphere surface carboxyl groups, hydroxyl and carbonyl, pass through Boehm titration measuring.
In the present invention, the carbosphere can be adopted and be prepared with the conventional methods in the field.It is described under preferable case
Carbosphere is prepared by biomass by hydro-thermal method.The biomass is preferably selected from glucose, fructose, chitosan, sucrose, β-
At least one of cyclodextrin, starch and cellulose.
Preferably, the step of hydro-thermal method includes: to disperse biomass in a solvent, to form uniform and stable solution;
Then the solution is subjected to hydro-thermal reaction;Product after hydro-thermal reaction is centrifuged, washed, is dried.It is described in the present invention
" solution " refers to biomass and the uniform and stable mixed liquor that solvent is formed, and can be solution or suspension.Preferably, described
Solvent is selected from water and/or ethyl alcohol.Preferably, relative to the solvent of 100mL, the amount of the biomass is 5-15g.
According to the present invention, the hydro-thermal reaction can carry out in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining.
Preferably, the temperature for carrying out the hydro-thermal reaction is 160-320 DEG C;Reaction time is 4-30h, preferably 6-24h.
A kind of preferred embodiment according to the present invention, the biomass contain cellulose, carry out the reaction of hydro-thermal reaction
Temperature is 215-320 DEG C, preferably 230-300 DEG C.
Another preferred embodiment according to the present invention, the biomass be selected from glucose, fructose, chitosan, sucrose,
At least one of beta-cyclodextrin and starch, the reaction temperature for carrying out hydro-thermal reaction is 160-240 DEG C.
According to the present invention, dark brown suspension is obtained after the completion of hydro-thermal reaction, it can be centrifuged, be washed and be dried
To obtain carbosphere.The method for being centrifuged, being washed and being dried can be method commonly used in the art, and the present invention does not limit herein
It is fixed.
Second aspect of the present invention provides a kind of high temperature aqueous-based drilling fluid, the high temperature aqueous-based drilling fluid contain water, bentonite,
Carbosphere, high temperature shale control agent, high temperature fluid loss additive, lubricant, flow pattern regulator, high-temperature stabilizer and weighting material,
In, the average grain diameter of the carbosphere is 50-50000nm, oxygen-containing functional group total amount >=0.2mmol/g.
In the present invention, the high temperature shale control agent can be polyoxyethylene imines and molecule of the molecular weight less than 1000
It measures one or more of in the cycloalkanes amine less than 1000;The high temperature fluid loss additive can be sulfonated phenolic resin SMP, sulfonated lignite
One or more of resin SPNH, Driscal-D and Dristemp;The lubricant can for mineral oil, elastic graphite and
One of expansible graphite is a variety of;The flow pattern regulator can be amphoteric ion polymer XY-27, zwitterion polymerization
It is one or more of in object XY-28, amphoteric ion polymer FA367 and co-polymer of sulfonate;The high-temperature stabilizer can be Asia
One or more of sodium sulphate and thiocarbamide;The heavy weight additive can be one in barite, calcium carbonate, Iron Ore Powder and formates
Kind is several.The high temperature shale control agent, the high temperature fluid loss additive, the lubricant, the flow pattern regulator, the height
Warm stabilizer and the weighting material can be commercially available, and dosage can be the conventional selection of this field.
The preparation method of carbosphere involved in carbosphere involved in second aspect of the present invention and first aspect present invention
Etc. features correspond to it is identical, in order to avoid repeat, the present invention therefore not to repeat here.
Preferably, relative to the water of 100mL, the content of the carbosphere is 0.1-5g.It is further preferred that relative to
The content of the water of 100mL, the carbosphere is 0.3-3g, is still more preferably 0.5-1.5g.
Compared with prior art, the invention has the following beneficial effects:
(1) traditional sealing agent often degrades or fails at high temperature, it is difficult to it plays a role, and carbosphere is in 200 DEG C of height
The lower performance of temperature is highly stable, can still block to mud shale micropore.
(2) conventional inorganic nano sealing agent, such as nano silica, nanometer calcium carbonate are added in drilling fluid and easily send out
It is raw to reunite, to lose the feature of nano particle, and then it is difficult to effectively play the superiority of nano particle, and carbosphere surface is rich
The oxygen-containing functional groups such as hydroxyl, carboxyl and carbonyl can preferably be dispersed in water holding dispersion stabilization, meanwhile, carbosphere can
The effects of forming hydrogen bond by the siloxy of the clay particle in surface functional group and drilling fluid, improves the rheological characteristic of system.
(3) from a wealth of sources since the raw material for preparing carbosphere is biomass, it is environmental-friendly, and preparation process is simple.It adopts
During preparing carbosphere with hydro-thermal method, absolutely not introduces any noxious material and participate in reaction, guarantee entire reaction process
It is all asepsis environment-protecting that is environmentally protective, therefore also ensuring product carbosphere.
The present invention will be described in detail by way of examples below.In following preparation example and embodiment, such as without special theory
It is bright, it is conventional method;The reagent and material commercially obtain unless otherwise specified.
In following preparation example, using NanoBrookOmni multi-angle granularity and the highly sensitive Zeta potential analyzer (U.S.
Brookhaven company) test carbosphere particle diameter distribution, test method are as follows: carbosphere is add to deionized water and is configured to
0.1% suspension is tested immediately after ultrasonic disperse 10min.
Carbosphere surface functional group analysis use Boehm titration, i.e., with NaOH solution neutralization number indicate carboxyl, hydroxyl and
Carbonyl total content.With reference to the test side in " measurement of several activated carbon surface acidic-groups and its influence to absorption property "
Method, specific steps are as follows: the carbosphere for weighing 1.0g or so is put into the conical flask with plug, adding 25mL concentration is
The NaOH solution of 0.1N.Conical flask is placed on Kang Shi oscillator after shaking 1h and removes the filtering, with appropriate in being stored at room temperature for 24 hours
Deionized water washing filter paper and carbosphere are to wash filtrate for the free excess base in surface.50mL is added into filtrate, 0.1N's
Hydrochloric acid solution.It is micro- red to solution with the standard NaOH solution back titration excess acid of 0.1N with phenolphthalein indicator.
Preparation example 1
The beta-cyclodextrin of 25g is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydro-thermal
It in reaction kettle, is put into oil bath pan, reacts 30h at 160 DEG C.It is cooled to room temperature to it, the dark brown generated after reaction is hanged
Floating solution is centrifuged 20min at 15000rpm, and the precipitating that centrifugation obtains is used dehydrated alcohol and deionized water ultrasound respectively, from
The heart, washing three times, resulting dark brown precipitating are placed in baking oven, dries at 60 DEG C, obtains fluffy black powder object
Matter, i.e. carbosphere, are denoted as CMS-1, and measuring its average grain diameter is 246nm, and oxygen-containing functional group total amount is 0.214mmol/g.
Preparation example 2
5g fiber cotton pulp (cellulose) is dispersed in 100mL deionized water, 2h is stirred with the rate of 500rpm under room temperature
Milky paste system is obtained, the hydrothermal reaction kettle for being transferred to volume after cell disruptor ultrasound 10min as 250mL is then used
In, it is 300 DEG C of reaction 8h that in-furnace temperature is controlled in high temp roller heating furnace, then cooled to room temperature, will be raw after reaction
At dark brown aaerosol solution be centrifuged 20min at 15000rpm, the precipitating being centrifuged uses dehydrated alcohol and deionization respectively
Water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried at 50 DEG C, is obtained fluffy black powder
Last shape substance, i.e. carbosphere, are denoted as CMS-2, and measuring its average grain diameter is 409nm, and oxygen-containing functional group total amount is 0.254mmol/
g。
Preparation example 3
75g soluble starch is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydro-thermal
It in reaction kettle, is put into high temp roller furnace, sets roller furnace heating temperature as 180 DEG C, react 6h at 180 DEG C.It is down to it
After room temperature, the dark brown aaerosol solution generated after reaction is centrifuged 20min at 15000rpm, the precipitating being centrifuged is used respectively
Dehydrated alcohol and deionized water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried at 80 DEG C,
Fluffy black powder substance, i.e. carbosphere are obtained, CMS-3 is denoted as, measuring its average grain diameter is 1386nm, oxygen-containing functional group
Total amount is 0.221mmol/g.
Infrared spectrum analysis is carried out to CMS-3, as a result as shown in Figure 1.It will be seen from figure 1 that 3381cm-1For surface hydroxyl
The stretching vibration absworption peak of base-OH, 2900cm-1For the stretching vibration absworption peak of C-H, 1703cm-1For carboxylic acid carbonyl C=O vibration
Absorption peak, 1612cm-1Corresponding conjugated alkene skeletal vibration peak, 1022cm-1Make vibration absorption peak for C-O-C mind.Above-mentioned functional group
Presence, the carbosphere after showing carbohydrate carbonization remains a large amount of functional group's groups in carbohydrate molecule, and carbohydrate is in hydrolytic process
In be likely to occur a degree of aromatization because carbohydrate molecule occur between each other in hydro-thermal reaction dehydrating condensation and crosslinking
Reaction forms carbon-carbon double bond and C=O bond, so that carbonization obtains carbosphere.The functional group of carbosphere mainly with-OH, C=O ,-
Dehydrating condensation and aromatic ring two processes have occurred based on COOH oxygen-containing functional group, in hydrothermal reaction process.These oxygen-containing functions
Group can be improved the hydrophily and stability, dispersibility in aqueous solution of carbosphere, for its functionally using laying
Basis.
Preparation example 4
50g glucose is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydro-thermal reaction
It in kettle, is put into high temp roller furnace, sets roller furnace heating temperature as 190 DEG C, react 12h at 190 DEG C.Room temperature is down to it
Afterwards, the dark brown aaerosol solution generated after reaction is centrifuged 20min at 15000rpm, the precipitating being centrifuged is used anhydrous respectively
Ethyl alcohol and deionized water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried, is obtained at 60 DEG C
Fluffy black powder substance, i.e. carbosphere, are denoted as CMS-4, and measuring its average grain diameter is 1097nm, oxygen-containing functional group total amount
For 0.216mmol/g.
Preparation example 5
40g fructose is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydrothermal reaction kettle
In, it is put into high temp roller furnace, sets roller furnace heating temperature as 200 DEG C, react 8h at 200 DEG C.It is cooled to room temperature to it,
The dark brown aaerosol solution generated after reaction is centrifuged 20min at 15000rpm, the precipitating being centrifuged uses anhydrous second respectively
Pure and mild deionized water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried, is obtained fluffy at 60 DEG C
The black powder substance of pine, i.e. carbosphere, are denoted as CMS-5, and measuring its average grain diameter is 821nm, and oxygen-containing functional group total amount is
0.223mmol/g。
Preparation example 6
48g chitosan is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydro-thermal reaction
It in kettle, is put into high temp roller furnace, sets roller furnace heating temperature as 160 DEG C, react 16h at 160 DEG C.Room temperature is down to it
Afterwards, the dark brown aaerosol solution generated after reaction is centrifuged 20min at 15000rpm, the precipitating being centrifuged is used anhydrous respectively
Ethyl alcohol and deionized water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried, is obtained at 60 DEG C
Fluffy black powder substance, i.e. carbosphere, are denoted as CMS-6, and measuring its average grain diameter is 356nm, oxygen-containing functional group total amount
For 0.247mmol/g.
Preparation example 7
48g chitosan is weighed, high-speed stirred is dispersed in 500mL deionized water, which is transferred to hydro-thermal reaction
It in kettle, is put into high temp roller furnace, sets roller furnace heating temperature as 160 DEG C, react 16h at 160 DEG C.Room temperature is down to it
Afterwards, the dark brown aaerosol solution generated after reaction is centrifuged 20min at 15000rpm, the precipitating being centrifuged is used anhydrous respectively
Ethyl alcohol and deionized water ultrasound, centrifugation, three times, resulting dark brown precipitating is placed in baking oven for washing, is dried, is obtained at 60 DEG C
Fluffy black powder substance, i.e. carbosphere, are denoted as CMS-7, and measuring its average grain diameter is 258nm, oxygen-containing functional group total amount
For 0.301mmol/g.
Embodiment 8
Bentonite base slurry is prepared according to the method for embodiment 1, is added obtained in 4g preparation example 3 into bentonite base slurry
CMS-3,2g polyoxyethylene imines (molecular weight 1800 is purchased from Shanghai Aladdin biochemical technology limited liability company), 12g sulfonation
Phenolic resin SMP, 12g mineral oil, 4g amphoteric ion polymer XY-27,4g sodium sulfite and 120g barite are configured to drilling well
Liquid Z1.By drilling fluid, heat rolling 16h, heat will be bored slurries after rolling and is cooled to room temperature, stirs in 10000r/min under the conditions of 200 DEG C
API filtration (the FL of slurries is tested after 10minAPI), test result is as shown in table 4.
Comparative example 1-4
It carries out according to the method for embodiment 1, unlike, the carbon nanometer micro ball in embodiment 1 is replaced into nanometer two respectively
Silica sealing agent (partial size 12nm is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd.), nanometer polymer microballoon MAX-
SHIELD (partial size 100-400nm is purchased from Baker Hughes Inc), low Poison sulfonated gilsonite DYFT are (purchased from the macro diligent petroleum in Beijing
Auxiliary agent Co., Ltd), sulfonated lignite resin SPNH (be purchased from Beijing Hong Qin petroleum assistant Co., Ltd), drilling fluid nanoemulsions
(average grain diameter 120nm is purchased from Shengli Chemical Company Ltd. Of Slof., Dongying city).Test result such as table 1
To shown in table 3.
Comparative example 5
The performance bored slurries and test drilling fluid is prepared according to the method for embodiment 8.Unlike, CMS-3 is replaced with
Nano silica sealing agent (partial size 12nm is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd.), obtains drilling fluid Z2,
The results are shown in Table 4.
Table 1
It can be seen that in 4% bentonite base slurry that be separately added into carbon obtained in preparation example 1-7 micro- from 1 test result of table
After ball CMS-1 to CMS-7, the API filtration of 160 DEG C of heat rolling rear slurries is remarkably decreased, and the minimum 48.4mL that can be starched by base drops
Rheological characteristic (apparent viscosity, plastic viscosity and yield value) down to 10.6mL, and heat rolling rear slurry maintains more reasonable range,
And other sealing agents such as nano silica is added, API filtration is up to 46.4mL after 160 DEG C of heat rollings, illustrates it substantially not
Has plugging effect.The API filtration of slurries can be effectively reduced before the rolling of MAX-SHIELD heat, but API filtration rises after heat rolling
To 28.8mL, this is because caused by its high-temperature stability is deteriorated.Again it can be seen that the system of nanoemulsions is added after heat rolling
API filtration is even higher than base slurry, illustrates that it has completely lost stability at high temperature, can not play its plugging action.It passes
Filter loss can be effectively reduced before the sulfonated gilsonite DYFT heat rolling of system, but filter loss also dramatically increases after heat rolling.Sulfonated lignite resin
It is kept before the rolling of SPNH heat compared with low filtration loss, filter loss is relatively low after heat rolling, but is still higher than carbosphere of the present invention.Thus
As can be seen that carbosphere used in the present invention remains to that filter loss is effectively reduced as sealing agent at high temperature, plays to block and make
With.
Table 2
From 2 test result of table it is found that after warm rolling 16h 200 DEG C high, conventional nanometer sealing agent such as nano silica,
MAX-SHIELD and nanoemulsions lose thermal stability, and the API filtration after heat rolling increases considerably, or even considerably beyond
The filter loss of bentonite base slurry, and then significantly reduced added with the slurries filter loss of carbosphere, the minimum 24mL that can be down to, it is seen that
It still maintains performance under high temperature to stablize, and performance is more preferable compared with SPNH and DYFT grade height temperature drop fluid loss agents.
Table 3
Test sample |
Passing time/s |
Rock sample permeability/D |
Permeability decrease rate/% |
Clear water (blank sample) |
310 |
4.98×10-6 |
- |
CMS-1 |
6150 |
3.26×10-7 |
93.5 |
CMS-2 |
5500 |
7.5×10-7 |
84.9 |
CMS-3 |
6670 |
2.75×10-7 |
94.5 |
CMS-4 |
4890 |
9.1×10-7 |
81.7 |
CMS-5 |
7250 |
2.42×10-7 |
95.1 |
CMS-6 |
7610 |
2.36×10-7 |
95.3 |
CMS-7 |
6620 |
2.01×10-7 |
96.0 |
Nano silica |
3400 |
2.28×10-6 |
54.2 |
MAX-SHIELD |
560 |
3.77×10-6 |
24.3 |
DYFT |
3550 |
1.52×10-6 |
69.5 |
Nanoemulsions |
750 |
4.02×10-6 |
19.3 |
It can be seen that clear water rapid osmotic in mud shale hole from 3 test result of table to migrate, cause pressure in 310s
It is transmitted to downstream from the upstream of rock sample, and added with the 160 DEG C high slurries for warming the different sealing agents after rolling and mud shale surface
After effect, pressure penetration time change is different.After wherein carbosphere obtained in preparation example and mud shale act on, pressure transmitting
Time extends to 4890-7610s by 310s, and the permeability decrease of mud shale rock sample reaches 81.7-96.0%, shows that it is effectively sealed
The micro-nano hole of mud shale is blocked up, pressure transmitting effect has been delayed in resistance.And added with the test fluid and mud shale of nano silica
After effect, rock sample permeability decrease rate is only 54.2%, and nanometer polymer microballoon and nanoemulsions have lost after high temperature action
Sealing characteristics is lost, rock sample permeability decrease rate shows preferably to hinder slow pressure transmitting effect less than 30%, DYFT, but itself and mud
After shale effect, permeability decrease rate is only 69.5%.It can be seen that carbosphere still shown after high temperature action it is very excellent
Closure mud shale micropore, hinder the effect of slow pore pressure transmitting, can be used as sealing agent in drilling fluid, be a kind of property
It can very superior micro-nano plugging material.
Table 4
Test sample |
API filtration/mL after the rolling of 200 DEG C/16h heat |
Drilling fluid Z1 |
6.2 |
Drilling fluid Z2 |
16.4 |
From the results shown in Table 4, drilling fluid of the invention has lower filter loss at 200 DEG C, has preferable
High temperature resistant property.
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.