CN109468123A - A kind of drilling fluid environmental protection polymer micro Nano material and preparation method thereof - Google Patents
A kind of drilling fluid environmental protection polymer micro Nano material and preparation method thereof Download PDFInfo
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- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
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Abstract
The invention discloses a kind of drilling fluid environmental protection polymer micro Nano materials and preparation method thereof.The polymer for drilling fluid micro Nano material has good dehydration control and shut-off capacity, and biological degradability is good, and environmental-protecting performance is excellent；Environmental protection polymer micro Nano material can substitute the clay in drilling fluid, it is formed with conducive to the drilling fluid being separated by solid-liquid separation, in the case where meeting conventional drilling job requirements, so that later period offal treatment becomes simply, the environmental issues such as discharge and the waste treatment of drilling fluid can be effectively solved.
Description
Technical field
The invention belongs to oil field, it is related to a kind of drilling fluid environmental protection polymer micro Nano material and preparation method thereof.
Background technique
With the rapid development of World Oil Industry, the progress of modern environmental protection concept and the development of environmental protection cause are to drilling well skill
Art proposes the requirement of more Gao Gengxin.During oil gas drilling, drilling fluid is as the first entry well fluid, to oil-gas Layer reality
It is played a crucial role during applying protection.The rejected well drilling liquid generated during exploration and development simultaneously, due to it
Containing there are many chemical treatments, pollution is caused to the ecological environment of surrounding, also brings inconvenience to subsequent job, is easy to make
At adverse consequences such as environmental dispute and economic losses.Especially in Development of Drilling Fluids by environmental protection policy and law, regulation
In the case where limitation, research, which meets the New well drilling liquid system that drilling engineering technology and environmental protection need and just seems, more must
It wants.
The processing of domestic and international oil gas field rejected well drilling liquid, which is generally taken, to be first separated by solid-liquid separation, then respectively to liquid and solid slag
It is handled, but waste water-base drilling liquid at this stage is mostly the high dispersion of stability, is separated by solid-liquid separation difficult；Solid-liquid
After separation due to clay particle aquation and irreducible water exist, make processing after solid phase moisture content 80% or more, seriously
Influence the post-processing of rejected well drilling liquid.
Summary of the invention
The object of the present invention is to provide a kind of drilling fluid environmental protection polymer micro Nano materials and preparation method thereof.
Polymer for drilling fluid micro Nano material provided by the invention is made by the raw material of following each mass parts:
In above-mentioned polymer for drilling fluid micro Nano material, the inorganic nano-particle is chosen in particular from nanometer calcium carbonate, covers
At least one of de- soil, nano silica and nano-titanium dioxide；
The partial size of the inorganic nano-particle is specially 10-100nm；
The surfactant is chosen in particular from neopelex, lignosulfonates and fatty alcohol polyoxyethylene ether
At least one of sodium sulfate salt；The lignosulfonates are specially sodium lignin sulfonate；
The natural polymer is chosen in particular from least one of cellulose, lignin, starch and chitosan；The fiber
Element is specially polyanion cellulose；The starch is specially cornstarch；
The copolyreaction monomer is chosen in particular from acrylic acid (AA), acrylamide (AM), Methacrylamide (MAM) and first
At least one of base hydroxy-ethyl acrylate (HEMA)；
The crosslinking agent is chosen in particular from N,N methylene bis acrylamide, divinylbenzene, dicthenone and glycerol extremely
Few one kind；
The initiator is chosen in particular from least one of ammonium persulfate, sodium sulfite and sodium thiosulfate；
The water is specially deionized water.
Specifically, the polymer for drilling fluid micro Nano material is polymer for drilling fluid micro Nano material a, drilling fluid
With polymer micro-nanometer material b or polymer for drilling fluid micro Nano material c；
Wherein, polymer for drilling fluid micro Nano material a is to be made by the raw material of following each mass parts:
The polymer for drilling fluid micro Nano material b is to be made by the raw material of following each mass parts:
The polymer for drilling fluid micro Nano material c is to be made by the raw material of following each mass parts:
The method provided by the invention for preparing the polymer for drilling fluid micro Nano material, includes the following steps:
1) according to the proportion in the polymer for drilling fluid micro Nano material, by inorganic nano-particle, surfactant,
Copolyreaction monomer and 100-500 parts of water mix, and obtain nano-dispersed suspension；
2) according to the proportion in the polymer for drilling fluid micro Nano material, the natural polymer is dissolved in 100-
500 parts of water adjust pH value after 9-10, to add crosslinking agent and carry out cross-linking reaction, obtain natural polymer aqueous solution；
3) the natural polymer aqueous solution is mixed with the nano-dispersed suspension in an inert atmosphere, is added
Initiator is warming up to 60-100 DEG C (concretely 80 DEG C) reaction 3-4h；End of reaction obtains the polymer for drilling fluid micro-nano
Rice material.
The method also includes following steps: the step 3) after completion of the reaction, reaction product is washed, dry, powder
It is broken.
In the washing step, detergent is ethyl alcohol；
In the baking step, temperature 70-90.℃
In step 2) the cross-linking reaction step, temperature be 50-120 DEG C, specially 80 DEG C, time 30-60min；
In the step 3), inert atmosphere is nitrogen atmosphere.
In addition, the polymer for drilling fluid micro Nano material that aforementioned present invention provides in drilling well or prepares answering in drilling fluid
With also belonging to protection scope of the present invention.Wherein, the drilling well or the method for preparing drilling fluid, including the following steps: will be described
Polymer for drilling fluid micro Nano material is added to drilling well liquid-based slurry；
The additional amount of the polymer for drilling fluid micro Nano material is specially 1-3g:100ml.
The present invention is from the environmental protection of drilling fluid and the angle of post-processing, by researching and developing polymer micro-nanometer material
As New drilling fluid basic material, from setting about solving in terms of clay and degradable two being separated by solid-liquid separation problem in offal treatment
And environmental issue；Under the conditions of can satisfy conventional drilling job requirements, solves solid-liquid in the offal treatment of drilling fluid later period
Separation problem effectively solves the environmental issues such as discharge and the waste treatment of drilling fluid.Polymer for drilling fluid provided by the invention
Micro Nano material has good dehydration control and shut-off capacity, and biological degradability is good, and environmental-protecting performance is excellent；Environmental protection polymer is micro-
Nano material can substitute the clay in drilling fluid, be formed with conducive to the drilling fluid being separated by solid-liquid separation, meeting conventional drilling operation
In the case where demand, so that later period offal treatment becomes simply, discharge and waste treatment of drilling fluid etc. can be effectively solved
Environmental issue.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
In following embodiments, polyanion cellulose used is purchased from Luzhou north Qiao Feng Chemical Co., Ltd.,；Cornstarch used is purchased from
Hebei De Rui starch Co., Ltd.
Embodiment 1,
Polymer for drilling fluid micro Nano material a is to be made by the raw material of following each mass parts:
Partial size is the nano silica 60 of 10-100nm
1) by 60 parts of nano silica, 0.01 part of neopelex, 300 parts of deionized water, acrylic monomers 5
Part is added in four-hole boiling flask, stirs, and forms nano-dispersed suspension；
2) by 30 parts of polyanion cellulose, 300 parts of configuration solution of deionized water adjust pH value of solution with sodium hydroxide solution
Value is 9-10, adds N, 0.2 part of N- methylene-bisacrylamide, 80 DEG C of cross-linking reaction 30min, is cooled to room temperature, forms day
Right water-soluble polymers；
3) natural polymer aqueous solution is added in four-hole boiling flask and is mixed with nano-dispersed suspension, in logical condition of nitrogen gas
Under, 30min is stirred, 0.08 part of ammonium persulfate is then added, is warming up to 80 DEG C of reaction 3-4h；After reaction, by product second
Alcohol washing, 70-90 DEG C drying to constant weight, finally crushes and obtains environmental protection polymer micro Nano material provided by the invention.
Embodiment 2
Polymer for drilling fluid micro Nano material b is to be made by the raw material of following each mass parts:
Partial size is the nano silica 40 of 10-100nm
Preparation method is same as Example 1, only obtains each raw material and its dosage according to replacing listed by embodiment 2.
Embodiment 3
Polymer for drilling fluid micro Nano material c is to be made by the raw material of following each mass parts:
Preparation method is same as Example 1, only obtains each raw material and its dosage according to replacing listed by embodiment 3.
Petroleum Group standard " the Q/SY 111-2007 referring in of environmental protection polymer micro Nano material prepared by embodiment 1-3
Oilfield Chemicals, drilling fluid bio-toxicity classification and detection method Luminous bacteria ", " GB11914-89 water chemical oxygen demand
(CODcr) measurement potassium dichromate method " and " measurement of HJ 505-2009 water quality five-day BOD (BOD5) is diluted and is connect
Kind method " come the environmental-protecting performance for material of grading.Its toxic grade and degradability specifically divide as shown in the table below:
Table 1, bio-toxicity grade
| Bio-toxicity grade | Photobacteria EC50(mg/L) |
| Severe toxicity | < 1 |
| Weight poison | 1~100 |
| Poisoning | 101~1000 |
| Micro- poison | 1001~25000 |
| It is nontoxic | > 25000 |
Table 2, biological degradability grade
Table 3, the evaluation of the polymer micro-nanometer material feature of environmental protection
| Number | Bio-toxicity EC50 | Toxicity grading | Y=BOD5/CODCr(%) | Degradability classification |
| 1 | 187720 | It is nontoxic | 23.6 | It is more degradable |
| 2 | 227412 | It is nontoxic | 26.7 | It is degradable |
| 3 | 255540 | It is nontoxic | 28.3 | It is degradable |
From the point of view of the above experimental conditions, the environmental protection polymer micro Nano material of preparation is all non-toxic material, biological degradability
It is good, suitable for environmentally friendly drilling fluid system.
Embodiment 1-3 prepares drilling fluid by following below scheme by prepared environmental protection polymer micro Nano material and detects its property
Can, specific performance test reference GB/T 16783.1-2006 industrial gas oil drilling fluid on-the-spot test part 1: water base
Drilling fluid.
1, drilling fluid allocation program
1) it takes 400ml fresh water to stir in height and 0.8g sodium hydroxide, high-speed stirred 5min is added in cup；
2) under the conditions of 10000r/min high-speed stirred, environmental protection polymer micro Nano material made from 8g embodiment is added,
Height stirs 20min,
3) under the conditions of 10000r/min high-speed stirred, 1.2g polyanion cellulose, 4g carboxymethyl starch, 0.8g is added
Xanthan gum height stirs 20min；
4) under the conditions of 10000r/min high-speed stirred, 100g barite, high-speed stirred 20min is added；
5) base is prepared according to the above method and starch 3 glasss, be denoted as 1,2, No. 3 drilling fluid.
2, drilling fluid allocation program is compared
1) it takes 400ml fresh water to stir in cup addition 8g clay in height, stirs at low speed to being completely dispersed；
2) 0.8g sodium hydroxide is added, is conserved for 24 hours after high-speed stirred 20min；
3) the clay mixture 10000r/min high-speed stirred 10min that will have been conserved；
4) under the conditions of 10000r/min high-speed stirred, 1.2g polyanion cellulose, 4g carboxymethyl starch, 0.8g is added
Xanthan gum height stirs 20min；
5) under the conditions of 10000r/min high-speed stirred, 100g barite, high-speed stirred 20min is added；
6) 1 glass of drilling fluid is prepared according to the above method, is denoted as No. 4 drilling fluids (comparative sample).
3, drilling liquid performance evaluating
Testing performance of drilling fluid presses GB/T 16783.1-2006 industrial gas oil drilling fluid on-the-spot test part 1:
Water-base drilling fluid is evaluated, and acquired results are shown in Table 4.
Table 4, Evaluation results
No. 3 drilling fluids that environmental protection polymer micro Nano material prepared by embodiment 3 is prepared and No. 4 drilling wells prepared with clay
From the point of view of liquid comparative situation, polymer micro-nanometer material does not influence the traditional performance of entire drilling fluid system after replacing clay,
The rheological characteristic and dehydration control ability having had；After being separated by solid-liquid separation, the solid phase moisture content of No. 3 drilling fluids exists drilling fluid
42.7%, the solid phase moisture content of No. 4 drilling fluids is 62.5%, after illustrating that polymer micro-nanometer material replaces clay, wellbore fluid
System is separated by solid-liquid separation and becomes easy, and is conducive to later period offal treatment.Therefore, from the point of view of technology and Environmental-protection comprehensive, above-described embodiment
In polymer micro-nanometer material obtained, reach purpose of design requirement.
The present invention is not limited to above-mentioned preferred forms, and anyone should learn that the knots made under the inspiration of the present invention
Structure variation, the technical schemes that are same or similar to the present invention are fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of polymer for drilling fluid micro Nano material is made by the raw material of following each mass parts:
2. polymer for drilling fluid micro Nano material according to claim 1, it is characterised in that: the inorganic nano-particle
Selected from least one of nanometer calcium carbonate, montmorillonite, nano silica and nano-titanium dioxide；
The partial size of the inorganic nano-particle is 10-100nm；
The surfactant is selected from neopelex, lignosulfonates and sodium sulfate of polyethenoxy ether of fatty alcohol salt
At least one of；
The natural polymer is selected from least one of cellulose, lignin, starch and chitosan；
The copolyreaction monomer in acrylic acid, acrylamide, Methacrylamide and hydroxyethyl methacrylate extremely
Few one kind；
The crosslinking agent is selected from least one of N,N methylene bis acrylamide, divinylbenzene, dicthenone and glycerol；
The initiator is selected from least one of ammonium persulfate, sodium sulfite and sodium thiosulfate；
The water is deionized water.
3. polymer for drilling fluid micro Nano material according to claim 2, it is characterised in that: the lignosulfonates
For sodium lignin sulfonate；
The cellulose is polyanion cellulose；The starch is cornstarch.
4. polymer for drilling fluid micro Nano material according to claim 1 to 3, it is characterised in that: the drilling well
Liquid is polymer for drilling fluid micro Nano material a, polymer for drilling fluid micro Nano material b or brill with polymer micro-nanometer material
Well liquid polymer micro-nanometer material c；
Wherein, polymer for drilling fluid micro Nano material a is to be made by the raw material of following each mass parts:
The polymer for drilling fluid micro Nano material b is to be made by the raw material of following each mass parts:
The polymer for drilling fluid micro Nano material c is to be made by the raw material of following each mass parts:
5. a kind of method for preparing any polymer for drilling fluid micro Nano material in claim 1-4, including walk as follows
It is rapid:
1) according to the proportion in the polymer for drilling fluid micro Nano material any in claim 1-4, by inorganic nano-particle
Son, surfactant, copolyreaction monomer and 100-500 parts of water mix, and obtain nano-dispersed suspension；
2) according to the proportion in the polymer for drilling fluid micro Nano material any in claim 1-3, by the natural height
Molecule is dissolved in 100-500 parts of water, adjusts pH value after 9-10, to add crosslinking agent and carries out cross-linking reaction, obtains natural polymer
Aqueous solution；
3) the natural polymer aqueous solution is mixed with the nano-dispersed suspension in an inert atmosphere, adds initiation
Agent is warming up to 60-100 DEG C of reaction 3-4h；End of reaction obtains the polymer for drilling fluid micro Nano material.
6. according to the method described in claim 5, it is characterized by: the method also includes following steps: in the step 3)
After completion of the reaction, reaction product is washed, is dried, crushed.
7. according to the method described in claim 6, it is characterized by: detergent is ethyl alcohol in the washing step；
In the baking step, temperature is 70-90 DEG C.
8. according to the method any in claim 5-7, it is characterised in that: in step 2) the cross-linking reaction step, temperature
Degree is 50-120 DEG C or 80 DEG C, time 30-60min；
In the step 3), inert atmosphere is nitrogen atmosphere.
9. any polymer for drilling fluid micro Nano material in drilling well or prepares answering in drilling fluid in claim 1-4
With.
10. application according to claim 9, it is characterised in that: the drilling well or the method for preparing drilling fluid, including it is as follows
Step: the polymer for drilling fluid micro Nano material is added to drilling well liquid-based slurry；
The additional amount of the polymer for drilling fluid micro Nano material is 1-3g:100ml.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763327A (en) * | 2019-04-01 | 2020-10-13 | 中国石油化工股份有限公司 | Amphiphilic bottle brush type polymer and preparation method and application thereof |
| CN112266780A (en) * | 2020-10-13 | 2021-01-26 | 宁波锋成先进能源材料研究院有限公司 | Modified nano foam stabilizer and preparation method and application thereof |
| WO2021143549A1 (en) * | 2020-01-16 | 2021-07-22 | 四川格英达环保科技有限公司 | Harmless processing of sulfonated mud and drill cuttings dry solidified powder and preparation method thereof |
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| CN112266780B (en) * | 2020-10-13 | 2022-12-20 | 宁波锋成先进能源材料研究院有限公司 | Modified nano foam stabilizer and preparation method and application thereof |
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