CN106634895B - Biosynthesis base oil, shale gas drilling well biosynthesis basic ring protection drilling fluid and its preparation method and application - Google Patents
Biosynthesis base oil, shale gas drilling well biosynthesis basic ring protection drilling fluid and its preparation method and application Download PDFInfo
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- CN106634895B CN106634895B CN201611147389.8A CN201611147389A CN106634895B CN 106634895 B CN106634895 B CN 106634895B CN 201611147389 A CN201611147389 A CN 201611147389A CN 106634895 B CN106634895 B CN 106634895B
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- shale gas
- drilling fluid
- basic ring
- ring protection
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- 238000005553 drilling Methods 0.000 title claims abstract description 87
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 59
- 239000012530 fluid Substances 0.000 title claims abstract description 49
- 239000002199 base oil Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 12
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 34
- -1 unsaturated fatty acid methyl ester Chemical class 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007273 lactonization reaction Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 241000158728 Meliaceae Species 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical group [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 235000021081 unsaturated fats Nutrition 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 12
- 230000001851 biosynthetic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- XICHKUZHYIMXSQ-UHFFFAOYSA-N C(CCCCCCCCCCC)[Mg]C(C1=CC=CC=C1)(C)C Chemical compound C(CCCCCCCCCCC)[Mg]C(C1=CC=CC=C1)(C)C XICHKUZHYIMXSQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Classifications
-
- 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
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/34—Organic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of biosynthesis base oils, shale gas drilling well biosynthesis basic ring protection drilling fluid and its preparation method and application, belong to technical field of petroleum extraction, the active principle of biosynthesis base oil therein is polyglycerol fatty acid methyl esters, the structural formula of the polyglycerol fatty acid methyl esters are as follows:Here n is positive integer；The shale gas drilling well of biosynthesis base oil preparation of the invention is suitable for the exploitation of shale gas with biosynthesis basic ring protection drilling fluid, has the advantages that stable, environmental protection.
Description
Technical field
The present invention relates to technical field of petroleum extraction, use more particularly to a kind of biosynthesis base oil, shale gas drilling well
Biosynthesis basic ring protection drilling fluid and its preparation method and application.
Background technique
With the increasingly increase of petroleum resources demand, China accelerates the development and utilization to shale gas.But shale gas area
Block unconventional oil and gas extended reach well, horizontal well, directional well are more demanding to property of drilling fluid, are mainly manifested in the barefoot interval borehole wall
Stable problem is prominent, it is desirable that drilling fluid has stronger inhibition；Inclination section and horizontal segment plan rotary steerable tool, to drilling well
It is high that anti-collapse requirement is blocked up in fluid-tight；Horizontal segment is longer, requires lubricity higher.
The drilling fluid of shale gas block is most of at present all uses diesel oil base drilling fluid and high performance water-based drilling fluid, but bavin
Oil base drilling fluid is larger to environmental disruption, and the drilling cuttings generated is difficult to handle, and the temperature resistance of high performance water-based drilling fluid, inhibition
The performances such as property and lubricity are difficult to meet site operation requirement, are easy to happen the complex accidents such as reaming, bit freezing and setting of casing difficulty.
The problem of environmental disruption can be well solved using drilling fluid oily based on biodiesel, however bore at present
The biodiesel used in well liquid degradation easy to oxidize and slowly hydrolysis, stability is not strong, limits it in field of oil drilling
Use.
Summary of the invention
The purpose of the present invention is to provide a kind of biosynthesis base oil, shale gas drilling well biosynthesis basic rings to protect drilling well
Liquid and its preparation method and application, the shale gas drilling well biosynthesis base prepared with the biosynthesis base oil of the present patent application
Environmentally friendly drilling fluid stability is good, can be with effective protection oil and gas reservoir and environment.
The purpose of the present invention is what is be achieved through the following technical solutions:
In a first aspect, the embodiment of the present invention provides a kind of biosynthesis base oil, the biosynthesis base oil has
Effect group is divided into polyglycerol fatty acid methyl esters, the structural formula of the polyglycerol fatty acid methyl esters are as follows:
Here n is positive integer.
Further, mass percentage >=95% of the middle active principle of the biosynthesis base oil.
Second aspect, the embodiment of the present invention provide a kind of preparation method of biosynthesis base oil, include the following steps:
(1) unsaturated fatty acid methyl ester is subjected to itself lactonization reaction and obtains intermediate product；The intermediate product
Molecular formula are as follows:
It (2) is 15-20:1:10-15 according to mass ratio by unsaturated fatty acid methyl ester, perchloric acid and the intermediate product
Polymerization reaction is carried out, removes light component therein after the completion of the polymerization reaction to get the biosynthesis base oil, it is described
Biosynthesis base oil active principle be polyglycerol fatty acid methyl esters, the structural formula of the polyglycerol fatty acid methyl esters are as follows:
Here n is positive integer.
Further, the esterification reaction temperature is 70-80 DEG C, reaction time of esterification 3-5h.
Further, 160-180 DEG C of the polymeric reaction temperature, polymerization pressure 8-12MPa, polymerization reaction time
For 4-8h.
Further, the unsaturated fatty acid methyl ester is prepared by raw material of waste vegetable oil.
Further, the esterification using concentration for 65%-75% the concentrated sulfuric acid as catalyst.
The third aspect, the embodiment of the present invention provides a kind of shale gas drilling well biosynthesis basic ring protection drilling fluid, with volume
Percentage composition meter, the shale gas drilling well biosynthesis basic ring protection drilling fluid system includes following component:
Organoclay: 0.5-2%；
Primary emulsion: 1-3%, the primary emulsion are composed of the following components: emulsifier A: alkyl alcohol ethoxylates class
Nonionic surfactant；Emulsifier B: sulfonate；Emulsifier C: stearate and/or polyoxyethylene stearic acid ester；Emulsifier
A: emulsifier B: the mass ratio of emulsifier C is 1.5-2.5:0.8-1.2:1；
Auxiliary emulsifier: 1-3%；
Calcium oxide: 0.5-1%；
Fluid loss additive: 1-3%；
Heavy weight additive: 18-38%；
Surplus is the aqueous solution and above-mentioned biosynthesis base oil of calcium chloride；The concentration of the aqueous solution of the calcium chloride
For 25-35wt%；The volume ratio of the aqueous solution of the biosynthesis base oil and calcium chloride is 3-9:1.
Further, the organoclay is that the oleophylic that bentonite is formed after quaternary ammonium salt surface active agent is handled is viscous
Soil.
Further, the quaternary ammonium salt is dodecyl trimethyl ammonium bromide and/or dodecyl dimethyl Benzylmagnesium chloride
Ammonium.
Further, the emulsifier B is in mahogany acid iron, sodium alklyarylsulfonate and dialkyl succinylsuccinate ester sodium sulfonate
At least one.
Further, the stearate is zinc stearate.
Further, the polyoxy diene dioleate and HLB value that the auxiliary emulsifier is 7~8 with HLB value are 7~9
Polyoxypropylene stearate is mixed to prepare by the weight proportion of 1:1-3.
Further, the fluid loss additive is at least one of organic lignite, oxidized asphalt and emulsified asphalt.
Fourth aspect, the embodiment of the present invention provide a kind of preparation side of shale gas drilling well biosynthesis basic ring protection drilling fluid
Method obtains the shale gas drilling well biosynthesis basic ring protection drilling fluid after mixing above-mentioned component.
5th aspect, the embodiment of the present invention provide a kind of application of shale gas drilling well biosynthesis basic ring protection drilling fluid,
Above-mentioned drilling fluid is used in shale gas drilling well.
Compared with prior art, the present invention program at least has the following beneficial effects:
The preparation method of biosynthesis base oil of the present invention eliminates biodiesel by lactonization reaction and polymerization reaction
The unsaturated double-bond of unsaturated fatty acid methyl ester ultimately forms polyglycerol fatty acid methyl esters.The product has certain low-viscosity index, good
Characteristics, the pour points such as good biological degradability, good oxidation stability and excellent cryogenic property can reach -63 DEG C, and flash-point can
Reach 219 DEG C, is free of aromatic hydrocarbon, it is environmentally friendly.
This new bio synthetic oil diesel oil substitute is made into biosynthesis basic ring protection drilling fluid by the present invention, is used for shale gas
Block drilling well, is able to satisfy the drilling wells requirement such as temperature resistance, inhibition and lubrication, also has following advantage compared with diesel oil base drilling fluid:
1, the kinematic viscosity of this new bio synthetic oil is low compared with diesel oil, and under the conditions of same recipe, biosynthesis basic ring, which is protected, to be bored
The viscosity of well liquid also can be lower compared with diesel oil base drilling fluid, shows superior rheological characteristic, in drilling process, can improve machinery
Drilling speed and drilling efficiency.
2, this new bio synthetic oil is free of aromatic hydrocarbon, and the drilling cuttings that drilling well generates can be with direct emission, and treatment process is simple
It is convenient, reduce environmental pollution and disposal of cuttings expense.
3, the flash-point of this new bio synthetic oil is higher than diesel oil, and pour point is lower than diesel oil, its application range is expanded, extreme
Under the conditions of be also suitable.
Detailed description of the invention
Fig. 1 is biosynthesis base oil of the present invention, shale gas drilling well biosynthesis basic ring protection drilling fluid and its preparation side
2 shale expansion degree of contrast figure of system 1 and system in method.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below, but not as a limitation of the invention.
The present invention program eliminates the unsaturated double-bond in biodiesel fatty acid methyl esters by esterification and polymerization reaction,
Ultimately form polyglycerol fatty acid methyl esters.The product has certain low-viscosity index, good biological degradability, good oxidation stable
Property and characteristics, the pour point such as excellent cryogenic property can reach -63 DEG C, flash-point can reach 219 DEG C, aromatic hydrocarbon is free of, to environment friend
It is good.Specific parameters are shown in Table 1.
Table 1
Embodiment 1
The preparation process of emulsifier A are as follows: substitution reaction first occurs with ethylene oxide for laruyl alcohol, and reaction molar ratio is 1~3:
1, reaction condition are as follows: reacted 2~5 hours at a temperature of 100 DEG C~150 DEG C.Addition polymerization is ether to reaction product in turn, when in addition
After 10~15 to get arrive emulsifier A.Prepared emulsifier A shows preferable emulsifying capacity, wetting ability and biology drop
Solution ability.Laruyl alcohol in above-mentioned preparation process also can be replaced oleyl alcohol, cyclohexanol, stearyl alcohol.The preparation process of emulsifier B
Are as follows: three kinds of mahogany acid iron, sodium alkyl benzene sulfonate, dialkyl succinylsuccinate ester sodium sulfonate raw materials press 2:1:1 weight ratio, at 60 DEG C
High-speed stirred is uniformly mixed to arrive emulsifier B, and emulsifier B obtained is good oil soluble emulsifying agent, dispersing agent.Emulsification
Agent C is zinc stearate, with good thermal stability.
Emulsifier A obtained above, emulsifier B and emulsifier C are subjected to addition reaction, reaction by the mass ratio in table 1
Time is 2~8 hours, and reaction temperature is 100~200 DEG C, obtains 1#, 2#, 3# and 4# primary emulsion.Primary emulsion is added respectively
Entering to density is in 1.8g/cm3 oil base drilling fluid, and heat rolling 16h, carries out different primary emulsions at 65 DEG C at 150 DEG C
Performance evaluation, parameter testing the results are shown in Table 2.
Table 2
AV is apparent viscosity, referring to GB/T161782-1997, is measured with six speed rotational viscometer ZNN-D6B.
PV is plastic viscosity, referring to GB/T161782-1997, is measured with six speed rotational viscometer ZNN-D6B.
YP is yield value, referring to GB/T161782-1997, is measured with six speed rotational viscometer ZNN-D6B.
ES is emulsion-breaking voltage, is measured referring to GB/T161782-1997, electricity consumption stabilometer DWY.
As known from Table 2, by after three kinds of emulsifiers A, B and C 2:1:1 in mass ratio synthesis, viscosity effect is minimum, emulsion-breaking voltage
Highest forms a kind of dynamical primary emulsion, and emulsification well, wetting, dispersion can be played in oil base drilling fluid
Effect.
Embodiment 2
A kind of preparation method of biosynthesis base oil, includes the following steps:
1, by waste vegetable oil, unsaturated fatty acid methyl ester semi-finished product are made using prior art: by waste vegetable oil and
Dehydrated alcohol carries out esterification, and neutralization reaction then occurs with acid, product is distilled to obtain unsaturated fatty acid methyl ester
Semi-finished product；
2,500g unsaturated fatty acid methyl ester is weighed, is added in high pressure reaction assembly.
3, the concentrated sulfuric acid that 9g concentration is 65% is added into high pressure reaction assembly, as catalyst.
4, itself lactonization reaction is carried out, reaction temperature is 80 DEG C, reaction time 4h, constantly opens stirring in the process
Device.
5,100 DEG C after reaction, are continuously heating to, reaction product vapor is discharged, intermediate product is obtained；Is produced from centre
The molecular formula of object are as follows:
6, continue the high chlorine for 2000g unsaturated fatty acid methyl ester being added into high pressure reaction assembly and 100g concentration is 65%
Acid.
7, progress polymerization reaction, 180 DEG C of reaction temperature, reaction pressure 10MPa, reaction time 6h.
8, after reaction, reaction product is transferred in distillation still, is heated to 300 DEG C, light component is by steaming after distillation
It evaporates kettle to enter in light component receiving tank, during which constantly heat, when temperature rises to 350 DEG C, close light component receiving tank, open weight
After component receiving tank collects heavy constituent.Light component is the complete unsaturated fatty acid methyl ester of unreacted, and the recombination is divided into polyester
Fatty acid methyl esters, i.e. effective component in new bio synthetic oil finished product；Its molecular formula are as follows:
Here n is positive integer.
Embodiment 3
The preparation of biosynthesis basic ring protection drilling fluid system and performance comparison
The such as non-specified otherwise of following percentage refers both to percent by volume.
It is 4# primary emulsion obtained in embodiment 1 that system, which prepares primary emulsion used, and base oil used is to obtain in embodiment 2
The new bio synthetic oil arrived.
(1)1m3Biosynthesis basic ring protection drilling fluid system 1 is formulated are as follows:
1.5% organoclay；1.2% primary emulsion；2% auxiliary emulsifier；1.5% calcium oxide；3% filtrate reducing
Agent；The calcium chloride brine that new bio synthetic oil and concentration are 30wt%, the two volume ratio are 4:1；Remaining is barite, is aggravated
To density 2.1g/cm3。
(2)1m3Diesel oil base drilling fluid system 2 is formulated are as follows:
1.5% organoclay；1.2% primary emulsion；2% auxiliary emulsifier；1.5% calcium oxide；3% filtrate reducing
Agent；The calcium chloride brine that diesel oil and concentration are 30wt%, the two volume ratio are 4:1；Remaining is barite, is weighed out to density
2.1g/cm3。
The organoclay of above-mentioned two formula be parent that bentonite is formed after dodecyl trimethyl ammonium bromide is handled
Oily clay.Auxiliary emulsifier: the polyoxy diene dioleate that HLB value is 7.5 and the polyoxypropylene stearate that HLB value is 8 are selected
It is uniformly mixed in 1:2 ratio to get auxiliary emulsifier is arrived, auxiliary emulsifier can effectively change the wetability of system.In addition, auxiliary emulsifier
Better effect must be matched with primary emulsion.The effect of auxiliary emulsifier is that close heap composite membrane is formed in system, enhancing cream
Change effect.Fluid loss additive is organic lignite.
According to the formula of system 1-2, by each component high-speed stirred 1h or more, it is uniformly mixed and obtains biosynthesis basic ring guarantor
Drilling fluid system 1 and diesel oil base oil base drilling fluid system 2, and the heat rolling 16h at 150 DEG C respectively, carry out performance parameter test, ginseng
Number test result is shown in Table 3.
Table 3
Remarks: rheological characteristic test temperature is 65 DEG C ± 2 DEG C, and ES test temperature is 50 DEG C ± 2 DEG C, and HTHP test temperature is
150℃±2℃。
The ˊ parameter of G10 〞/10 is to ingress and egress, referring to GB/T161782-1997, with six fast rotational viscometer ZNN-D6B
It measures.
HTHP parameter is high temperature and high pressure filter loss, referring to GB/T161782-1997, with GGS42 type high pressure high temperature filter tester
It measures.
As known from Table 3, biosynthesis basic ring protection drilling fluid system can resist 150 DEG C of high temperature, compared with diesel oil base drilling fluid, viscosity and
Shear force is lower, shows superior rheological characteristic, is conducive to improve rate of penetration.
System 1 and the evaluation of 2 inhibition of system
Artificial core is suppressed first: mud shale is crushed, and crosses the sieve of 100 mesh；Sample after sieving is placed on (100 ± 3)
DEG C thermostatic drying chamber in dry 4 hours, be cooled to room temperature；Mud shale powder 10g is weighed to be packed into as test barrel diameter
Cylinder in, rock powder is paved；Load onto piston, be then placed on press machine gradually uniform pressurization until being indicated on pressure gauge
4MPa, pressure stabilizing 5 minutes；Pressure is shed, cylinder is removed, piston is slowly taken out from cylinder to get artificial core.
2 pieces of artificial cores are respectively put into shale expansion instrument, are separately added into 2 drilling fluid of system 1 and system, measurement is for 24 hours
The expansion height of shale.Measurement result is shown in Fig. 1.
From fig. 1, it can be seen that shale expansion height is all in biosynthesis environment protection drilling fluid system and diesel oil base drilling fluid system
It is smaller, stronger inhibition is shown, the demand of shale gas block drilling well high inhibition is able to satisfy.
System 1 and the evaluation of 2 lubricity of system
System 1 and system 2 are measured with extreme boundary lubrication instrument to the extreme boundary lubrication coefficient of the system respectively.Experimental result is shown in Table 4
Table 4
As known from Table 4, extreme boundary lubrication property coefficient all difference of system 1 and system 2 is smaller, and respectively less than 0.20, illustrate this hair
Bright biosynthesis basic ring protection drilling fluid system has good lubricity.
Above embodiments are only exemplary embodiment of the present invention, are not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can within the spirit and scope of the present invention make respectively the present invention
Kind modification or equivalent replacement, this modification or equivalent replacement also should be regarded as being within the scope of the present invention.
Claims (14)
1. a kind of preparation method of biosynthesis base oil, which comprises the steps of:
(1) unsaturated fatty acid methyl ester is subjected to itself lactonization reaction and obtains intermediate product；The molecule of the intermediate product
Formula are as follows:
It (2) is 15-20:1:10-15 progress according to mass ratio by unsaturated fatty acid methyl ester, perchloric acid and the intermediate product
Polymerization reaction, the polymerization reaction remove light component therein after the completion to get the biosynthesis base oil, the life
The active principle of object synthetic base oil is polyglycerol fatty acid methyl esters, the structural formula of the polyglycerol fatty acid methyl esters are as follows:
Here n is positive integer.
2. the preparation method of biosynthesis base oil according to claim 1, which is characterized in that the esterification temperature
Degree is 70-80 DEG C, reaction time of esterification 3-5h.
3. the preparation method of biosynthesis base oil according to claim 1, which is characterized in that the polymerization reaction temperature
160-180 DEG C, polymerization pressure 8-12MPa, polymerization reaction time 4-8h of degree.
4. the preparation method of biosynthesis base oil according to claim 1, which is characterized in that the unsaturated fat
Sour methyl esters is prepared by raw material of waste vegetable oil.
5. the preparation method of biosynthesis base oil according to claim 1, which is characterized in that the esterification with
The concentrated sulfuric acid that concentration is 65%-75% is catalyst.
6. a kind of shale gas drilling well biosynthesis basic ring protection drilling fluid, which is characterized in that described in terms of volumn concentration
Shale gas drilling well biosynthesis basic ring protection drilling fluid system includes following component:
Organoclay: 0.5-2%；
Primary emulsion: 1-3%, the primary emulsion are composed of the following components: emulsifier A: alkyl alcohol ethoxylates class it is non-from
Sub- surfactant；Emulsifier B: sulfonate；Emulsifier C: stearate and/or polyoxyethylene stearic acid ester；Emulsifier A: cream
Agent B: the mass ratio of emulsifier C is 1.5-2.5:0.8-1.2:1；
Auxiliary emulsifier: 1-3%；
Calcium oxide: 0.5-1%；
Fluid loss additive: 1-3%；
Heavy weight additive: 18-38%；
Surplus is the aqueous solution of calcium chloride and the biosynthesis basis that preparation method of any of claims 1-5 obtains
Oil；The concentration of the aqueous solution of the calcium chloride is 25-35wt%；The aqueous solution of the biosynthesis base oil and calcium chloride
Volume ratio be 3-9:1.
7. shale gas drilling well according to claim 6 biosynthesis basic ring protection drilling fluid, which is characterized in that described organic
Soil is the oleophylic clay that bentonite is formed after quaternary ammonium salt surface active agent is handled.
8. shale gas drilling well according to claim 7 biosynthesis basic ring protection drilling fluid, which is characterized in that the quaternary ammonium
Salt is dodecyl trimethyl ammonium bromide and/or dodecyl benzyl dimethyl ammonium chloride.
9. shale gas drilling well according to claim 6 biosynthesis basic ring protection drilling fluid, which is characterized in that the emulsification
Agent B is at least one of mahogany acid iron, sodium alklyarylsulfonate and dialkyl succinylsuccinate ester sodium sulfonate.
10. shale gas drilling well according to claim 6 biosynthesis basic ring protection drilling fluid, which is characterized in that described
Stearate is zinc stearate.
11. shale gas drilling well according to claim 6 biosynthesis basic ring protection drilling fluid, which is characterized in that described
The polyoxypropylene stearate that the polyoxy diene dioleate and HLB value that auxiliary emulsifier is 7~8 with HLB value are 7~9 is by 1:1-3
Weight proportion be mixed to prepare.
12. shale gas drilling well according to claim 6 biosynthesis basic ring protection drilling fluid, which is characterized in that the drop
Fluid loss agents are at least one of organic lignite, oxidized asphalt and emulsified asphalt.
13. a kind of preparation method of shale gas drilling well biosynthesis basic ring protection drilling fluid, which is characterized in that by claim 6-
12 described in any item components obtain the shale gas drilling well biosynthesis basic ring protection drilling fluid after mixing.
14. a kind of application of shale gas drilling well biosynthesis basic ring protection drilling fluid, which is characterized in that appoint claim 6-12
Drilling fluid described in meaning one is in shale gas drilling well.
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