CN110105929A - Solid lubricant for well drilling liquid polysaccharid derivative - Google Patents
Solid lubricant for well drilling liquid polysaccharid derivative Download PDFInfo
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- CN110105929A CN110105929A CN201910442742.2A CN201910442742A CN110105929A CN 110105929 A CN110105929 A CN 110105929A CN 201910442742 A CN201910442742 A CN 201910442742A CN 110105929 A CN110105929 A CN 110105929A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/02—Spotting, i.e. using additives for releasing a stuck drill
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/28—Friction or drag reducing 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/34—Lubricant additives
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Abstract
A kind of solid lubricant for well drilling liquid polysaccharid derivative, raw material: 30~40 parts of hydroxypropyl guar, 3~4 parts of propylene oxide, 0.1~0.15 part of sodium hydroxide, 20~30 parts of lauryl alcohol, 0.15~0.2 part of catalyst, 10~20 parts of white oil, 2~5 parts of surfactant, 0.1~2 part of defoaming agent, 10~20 parts of mica powder, 1~3 part of fungicide, 6~10 parts of ethyl alcohol, 10~25 parts of water.Preparation method: hydroxypropyl guar, sodium hydroxide, water being added in reaction kettle, continuously stirs, and propylene oxide is added, and stir, and flow back, reaction；Reaction solution is heated up, catalyst is added, is slowly stirred the lower mixed liquor that ethyl alcohol and lauryl alcohol is added, reaction；Reaction material liquid is cooled to room temperature, white oil, surfactant, defoaming agent, mica powder, fungicide is added, stirs evenly, it is dry, it is ground into a powder to obtain the final product.Lubricating coefficient reduced rate >=90% of the present invention has good high temperature filtration reduction and salt-resistance, and preparation condition is easy to reach, environmentally friendly.
Description
Technical field
The present invention relates to a kind of petroleum drilling fluid auxiliary agent, specifically a kind of solid lubricant for well drilling liquid polysaccharid derivative.
The invention further relates to the preparation methods of the solid lubricant for well drilling liquid polysaccharid derivative.
Background technique
Lubricant for drilling fluids is one of main inorganic agent of drilling fluid, is mainly used for reducing rubbing between drilling tool and the borehole wall
Resistance, to effectively avoid the generation of the down-hole accidents such as bit freezing.Recently as Holes of Complicated Wells such as deep-well, ultradeep well and extended reach wells
The appearance of body structure, the conditions such as high frictional resistance, high torque and the high temperature of drilling well propose the greasy property of lubricant for drilling fluids
Higher requirement.Meanwhile it is gradually stringent with world's environmental requirement, contaminated product measure causes to pay attention to extensively to the pollution of environment,
Contaminated product lubricant system is strictly prohibited.Environment-friendly and high-performance lubricant becomes the effective technology means of green, safe and efficient drilling well
One of.
Currently, the agent of drilling fluid green lubrication mainly has alcohol ethers, esters, amides, type of latex type etc., rub to the height at scene
Resistance problem proposes very good solution method.Alcohol ether series lubricant agent has apparent cloud point, turbid when being higher than its using temperature
When point temperature, lubricant effect is preferable.
Inventor retrieves following Relevant non-patent literature: such as " oilfield chemistry ", the 4th phase in 2002, New drilling fluid is used
One text of research of polyol ethers lubricant, describes author Xu Mingbiao etc. and has developed a kind of new multicomponent alcohol ether lubricant, should
Lubricant makes the lubricating coefficient of fresh-water drilling fluid decline 97%, and no biotoxicity.Ester lubricant is due to containing carbonyl in molecule
Base easily hydrolyzes in high temperature and water phase, therefore this series lubricant agent is under the high temperature conditions using limited.For another example " drilling fluid with
Completion fluid ", the 3rd phase of volume 32, in May, 2015, one text of research and application of new vegetable oil lubricant for drilling fluid describes work
Person Qi Ya male etc. obtain a kind of plant using vegetable fat and small molecular alcohol as raw material, and through surfactant and processing resistant to high temperatures
Oil lubricant makes drilling fluid extreme boundary lubrication coefficient decline 88.0%, and temperature resistance reaches 140 DEG C, and salt resistance is up to 10%, and compatibility is good
It is good.The vegetable oil amide series lubricant agent that vegetable oil is obtained through amidation process has good lubricity and the feature of environmental protection.For another example " west
Pacify University of Petroleum's journal (natural science edition) ", the 5th phase in 2017, environment-friendly type drilling well with the preparation of highly-efficient lubricant NH-HPL with
One text of performance evaluation describes expensive wide wait of author Lu and reacts oleic acid with polyetheramine to obtain lubricant, lubricating coefficient reduced rate
Up to 92.2%, temperature resistance is up to 160 DEG C, no biotoxicity, and influences on drilling fluid rheology and filtrate loss controllability very small.Lotion
Series lubricant agent ingredient is less, and property is stablized, also such as " oil and gas chemical industry ", the 4th phase in 2016, a kind of emulsion-type drilling fluid
One text of preparation and performance evaluation of lubricant, describing author Zhang Wen etc. by plant oleamide is main raw material, and enuatrol is emulsification
Agent is equipped with multiple auxiliary materials and obtains oil-in-water emulsion lubricant, which can resist 170 DEG C of high temperature, and salt tolerance is good.The above skill
Art solves the problems, such as that drilling rod and drilling tool are easy to wear, drilling well frictional resistance is big, compatibility drilling fluid is poor in drilling process, but still exists
The problem that heat and salinity tolerance ability is poor, lubricant effect is undesirable, thus research safety, efficiently, Environment-protecting Drilling Fluids with lubricator still
It is urgent problem.
Inventor retrieves following Patents documents: as CN109054777A discloses a kind of drilling fluid solid lubrication
Agent polysaccharid derivative and preparation method thereof, solid lubricant are made of following raw materials: 35 parts~45 parts polyethylene glycol 400s,
1 part~3 parts of boric acid, 1 part~2 parts of catalyst, 10 parts~20 parts of white oil, 2 parts~5 parts of surfactant, 1 part~3 parts of defoaming agent,
15 parts~25 parts of mica powder, 20 parts~30 parts of talcum powder.Preparation method: synthesis boric acid macrogol ester prepares solid lubricant.
This technology does not prepare traditional polysaccharid derivative, has only prepared solid lubricant.
Summary of the invention
Present invention purpose to be achieved is to provide a kind of solid lubricant for well drilling liquid polysaccharid derivative, it has good
Greasy property, while there is good high temperature filtration reduction, salt-resistance, easily biological-degradable performance.
For this purpose, a technical problem to be solved by this invention is, a kind of solid lubricant for well drilling liquid glycan is provided
The preparation method of derivative.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of solid lubricant for well drilling liquid polysaccharid derivative, its technical solution is that it is by following weight proportion (weight
Measure number or mass fraction) raw material made of: 30~40 parts of hydroxypropyl guar (powder), 3~4 parts of propylene oxide, hydroxide
0.1~0.15 part of sodium, 20~30 parts of lauryl alcohol, 0.15~0.2 part of catalyst, 10~20 parts of white oil, 2~5 parts of surfactant,
0.1~2 part of defoaming agent, 10~20 parts of mica powder, 1~3 part of fungicide, 6~10 parts of ethyl alcohol, 10~25 parts of water.The white oil
For the combination of one or both of No. 7 white oils, No. 10 white oils raw material, its proportion is arbitrary when two kinds of material combinations；It is described
Surfactant use one or both of OP-10 surfactant, AEO-9 surfactant raw material combination, two kinds
Its proportion is arbitrary when material combination；The catalyst is the group of one or more of sulfuric acid, hydrochloric acid, phosphoric acid raw material
It closes, its proportion is arbitrary when several material combinations.
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. reacting
Hydroxypropyl guar, sodium hydroxide, water is added by above-mentioned weight proportion in kettle, continuously stirs 25~30min at 25~30 DEG C, adds
Enter propylene oxide, stir, reflux, the reaction time is 3~4 hours, obtains reaction solution；2. 1. reaction solution that step is obtained heats up
To 40~45 DEG C, catalyst is added, is slowly stirred the lower mixed liquor that ethyl alcohol and lauryl alcohol is added, reacts 6~8 hours, obtains anti-
Answer feed liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, be added white oil, surfactant, defoaming agent, mica powder,
Fungicide stirs evenly, dry, is ground into a powder, as solid lubricant for well drilling liquid polysaccharid derivative (be ground into a powder, can be with
60 meshes are crossed to get solid lubricant for well drilling liquid polysaccharid derivative).
In above-mentioned technical proposal, preferred technical solution be can be, and in the catalyst, sulfuric acid is that molar concentration is
The aqueous sulfuric acid of 0.1mol/L；Above-mentioned hydrochloric acid is the aqueous hydrochloric acid solution that molar concentration is 0.1mol/L；Above-mentioned phosphoric acid is
Molar concentration is the phosphate aqueous solution of 0.1mol/L.Above-mentioned defoaming agent is polyoxyethylene oxypropylene glycerol, polydimethylsiloxanes
One of alkane.Above-mentioned polyoxyethylene oxypropylene glycerol can use polyoxyethylene oxypropylene glycerol GPE20, polyoxyethylene oxygen third
Alkene glycerol GPE20 is commercial goods, is produced by grand vertical coin chemical industry preparation Co., Ltd, Xinxiang City.Above-mentioned dimethyl silicone polymer
For commercial goods, the product of Shandong Xin Jie environmental protection technology Co., Ltd production can be used.Above-mentioned fungicide is modified for metronidazole
Bi-quaternary ammonium salt or starch preservative DL-D401, starch preservative DL-D401 manufacturer are moral oil blackeite works, are commercial goods,
Main component is 1,2- benzoisothiazolinone.The modified bi-quaternary ammonium salt of above-mentioned metronidazole is commercial goods, be can also refer to following
Document is produced: " Xi'an Petroleum University's journal (natural science edition) ", the 05th phase in 2009, author Zhou Juan etc., the double quaternary ammoniums of metronidazole
One text of the synthesis of salt and bactericidal property research.
In above-mentioned technical proposal, preferred technical solution be can be, and the solid lubricant for well drilling liquid glycan is derivative
Object is made of the raw material of following weight proportion: 30 parts of hydroxypropyl guar, 3 parts of propylene oxide, and 0.1 part of sodium hydroxide, 12
20 parts of alcohol, 0.15 part of catalyst, that is, sulfuric acid, 10 parts of white oil, 2.5 parts of surfactant, 1 part of defoaming agent, 10 parts of mica powder, sterilization
1 part of agent, 6 parts of ethyl alcohol, 20 parts of water；The white oil is the combination of two kinds of raw materials of No. 7 white oils and No. 10 white oils, and weight ratio is
1:1；The catalyst sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The surfactant is OP-10
The combination of two kinds of surfactant, AEO-9 surfactant raw materials, the weight of OP-10 surfactant and AEO-9 surfactant
The ratio between amount is 1: 1.5；The defoaming agent is polyoxyethylene oxypropylene glycerol GPE20；The fungicide is modified for metronidazole
Bi-quaternary ammonium salt.The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. anti-
It answers in kettle and 30 parts of hydroxypropyl guars, 0.1 part of sodium hydroxide, 20 parts of water is added by above-mentioned weight proportion, (at 25 DEG C at 25 DEG C
When) 30min (30 minutes) are continuously stirred, 3 parts of propylene oxide are added, stir, reflux, the reaction time is 3 hours, is reacted
Liquid；2. 1. reaction solution that step is obtained is warming up to 40 DEG C, 0.15 part of catalyst sulfuric acid is added, is slowly stirred 6 parts of second of lower addition
The mixed liquor of pure and mild 20 parts of lauryl alcohols reacts 6.5 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooling
To room temperature, 5 parts of No. 7 white oils, 5 parts of No. 10 white oils, 1 part of OP-10 surfactant, 1.5 parts of AEO-9 surfactants, 1 part are added
Defoaming agent polyoxyethylene oxypropylene glycerol GPE20,10 parts of mica powders, 1 part of fungicide, stir evenly, dry, are ground into a powder, i.e.,
For solid lubricant for well drilling liquid polysaccharid derivative.
In above-mentioned technical proposal, the preferred technical solution may also be that the solid lubricant for well drilling liquid glycan spreads out
Biology is made of the raw material of following weight proportion: 40 parts of hydroxypropyl guar, 4 parts of propylene oxide, and 0.15 part of sodium hydroxide, ten
25 parts of glycol, 0.2 part of catalyst, that is, phosphoric acid, 12 parts of white oil, 3 parts of surfactant, 2 parts of defoaming agent, 12 parts of mica powder, fungicide
2 parts, 8 parts of ethyl alcohol, 10 parts of water；The white oil is the combination of No. 7 white oils and No. 10 white oils, the weight of No. 7 white oils and No. 10 white oils
The ratio between amount is 1: 2；The catalyst phosphoric acid is the phosphate aqueous solution that molar concentration is 0.1mol/L；The surfactant
For OP-10 surfactant；The defoaming agent is dimethyl silicone polymer；The fungicide is starch preservative DL-
D401.The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
It is interior that 40 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 10 parts of water are added by above-mentioned weight proportion, it is continuously stirred at 30 DEG C
4 parts of propylene oxide are added in 30min, stir, reflux, and the reaction time is 4 hours, obtain reaction solution；2. 1. step is obtained anti-
It answers liquid to be warming up to 42 DEG C, 0.2 part of catalyst phosphoric acid is added, be slowly stirred the lower mixed liquor that 8 parts of ethyl alcohol and 25 parts of lauryl alcohols is added,
Reaction 8 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, 4 parts of No. 7 white oils and 8 parts are added
No. 10 white oils, 3 parts of OP-10 surfactants, 2 parts of defoaming agent dimethyl silicone polymers, 12 parts of mica powders, 2 parts of fungicide, stirring
Uniformly, dry, it is ground into a powder, as solid lubricant for well drilling liquid polysaccharid derivative.
In above-mentioned technical proposal, the preferred technical solution may also be that the solid lubricant for well drilling liquid glycan spreads out
Biology is made of the raw material of following weight proportion: 32 parts of hydroxypropyl guar, 3 parts of propylene oxide, and 0.15 part of sodium hydroxide, ten
20 parts of glycol, 0.15 part of catalyst, 15 parts of white oil, 3 parts of surfactant, 2 parts of defoaming agent, 10 parts of mica powder, 2 parts of fungicide,
8 parts of ethyl alcohol, 18 parts of water；The white oil is that No. 7 white oils are combined with No. 10 white oils, the weight ratio of No. 7 white oils and No. 10 white oils
It is 1: 2；The catalyst is the combination of two kinds of raw materials of hydrochloric acid and sulfuric acid, and weight ratio 1: 1, the hydrochloric acid is mole dense
Degree is the aqueous hydrochloric acid solution of 0.1mol/L, and the sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The table
Face activating agent is the combination of two kinds of OP-10 surfactant, AEO-9 surfactant raw materials, OP-10 surfactant, AEO-9
The weight ratio of surfactant is 1: 2；The defoaming agent is polyoxyethylene oxypropylene glycerol GPE20；The fungicide
For starch preservative DL-D401.The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative includes following technique
Step: 32 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 18 parts of water 1. are added by above-mentioned weight proportion in reaction kettle, in 25
30min is continuously stirred at DEG C, 3 parts of propylene oxide are added, is stirred, and reflux, the reaction time is 3.5 hours, obtains reaction solution；2. will
1. reaction solution that step obtains is warming up to 40 DEG C, and 0.075 part of hydrochloric, 0.075 part of sulfuric acid is added, is slowly stirred lower addition
The mixed liquor of 8 parts of ethyl alcohol and 20 parts of lauryl alcohols reacts 7 hours, obtains reaction material liquid；3. 2. reaction material liquid cooling that step is obtained
But to room temperature, 5 parts of No. 7 white oils, 10 parts of No. 10 white oils, 1 part of OP-10 surfactant, 2 parts of AEO-9 surfactants, 2 are added
Part defoaming agent polyoxyethylene oxypropylene glycerol GPE20,10 parts of mica powders, 2 parts of fungicide, stir evenly, dry, are ground into a powder,
As solid lubricant for well drilling liquid polysaccharid derivative.
In above-mentioned technical proposal, the preferred technical solution may also be that the solid lubricant for well drilling liquid glycan spreads out
Biology is made of the raw material of following weight proportion: 35 parts of hydroxypropyl guar, 3.5 parts of propylene oxide, and 0.12 part of sodium hydroxide,
28 parts of lauryl alcohol, 0.18 part of catalyst, that is, hydrochloric acid, 18 parts of white oil, 3.9 parts of surfactant, 0.15 part of defoaming agent, mica powder 16
Part, 2 parts of fungicide, 9 parts of ethyl alcohol, 22 parts of water；The white oil is the combination of two kinds of No. 7 white oils, No. 10 white oils raw materials, and No. 7 white
The weight ratio of oil and No. 10 white oils is 1: 2；The surfactant uses OP-10 surfactant, AEO-9 surface-active
The combination of two kinds of raw materials of agent, OP-10 surfactant, AEO-9 surfactant weight ratio be 1: 2；The catalyst
Hydrochloric acid is the aqueous hydrochloric acid solution that molar concentration is 0.1mol/L；The defoaming agent is dimethyl silicone polymer；The sterilization
Agent is the modified bi-quaternary ammonium salt of metronidazole.The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative includes following work
Skill step: being 1. added 35 parts of hydroxypropyl guars, 0.12 part of sodium hydroxide, 22 parts of water by above-mentioned weight proportion in reaction kettle,
30min is continuously stirred at 25 DEG C, 3.5 parts of propylene oxide are added, is stirred, reflux, the reaction time is 3.5 hours, obtains reaction solution；
2. 1. reaction solution that step is obtained is warming up to 40 DEG C, be added 0.18 part of hydrochloric, be slowly stirred it is lower be added 9 parts of ethyl alcohol and
The mixed liquor of 28 parts of lauryl alcohols reacts 7 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature,
6 parts of No. 7 white oils, 12 parts of No. 10 white oils, 1.3 parts of OP-10 surfactants, 2.6 parts of AEO-9 surfactants, 0.15 part are added
Defoaming agent dimethyl silicone polymer, 16 parts of mica powders, the modified bi-quaternary ammonium salt of 2 parts of fungicide metronidazoles, stir evenly, dry, grind
At powder, as solid lubricant for well drilling liquid polysaccharid derivative.
Above-mentioned hydroxypropyl guar belongs to polysaccharide (polysaccharid derivative), therefore obtained solid lubricant contains polysaccharid derivative.
Solid lubricant polysaccharid derivative of the invention has reached the good impact of performance, referring to the subsequent table of this specification
1, solid lubricant polysaccharid derivative performance of the invention are as follows: apparent viscosity variable quantity ± 2.0, lubricating coefficient reduced rate >=
90%.
Solid lubricant polysaccharid derivative of the invention is compared with the lubricant of the prior art with following good effect:
(1) solid lubricant has good greasy property, advantageously reduces bore hole friction resistance, is resistant to 190 DEG C of high temperature, and right
Apparent viscosity and the filter loss influence of drilling fluid are smaller, have the comprehensive performances such as good high temperature filtration reduction and salt-resistance, together
When have inhibition concurrently；(2) the solid profit polysaccharid derivative lubrication prescription working condition easily reaches, and property is stablized；(3) solid is poly-
Sugar derivatives lubricant is nontoxic and pollution-free, and easily biological-degradable is pollution-free to stratum, environmentally friendly.
Specific embodiment
To keep goal of the invention of the invention, technical solution and advantage clearer, below in conjunction with embodiment to the present invention
Technical solution carry out clear, complete description.Obviously, described embodiments are some of the embodiments of the present invention, Er Feiquan
Portion's embodiment.Based on the embodiment in invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1: solid lubricant for well drilling liquid polysaccharid derivative of the present invention is the original matched by following weight
Made of material: 30 parts of hydroxypropyl guar, 3 parts of propylene oxide, 0.1 part of sodium hydroxide, 20 parts of lauryl alcohol, catalyst, that is, sulfuric acid 0.15
Part, 10 parts of white oil, 2.5 parts of surfactant, 1 part of defoaming agent, 10 parts of mica powder, 1 part of fungicide, 6 parts of ethyl alcohol, 20 parts of water；Institute
The white oil stated is the combination of two kinds of raw materials of No. 7 white oils and No. 10 white oils, weight ratio 1: 1；The catalyst sulfuric acid is
Molar concentration is the aqueous sulfuric acid of 0.1mol/L；The surfactant is OP-10 surfactant, the surface AEO-9 is living
Property two kinds of raw materials of agent combination, the weight ratio of OP-10 surfactant and AEO-9 surfactant is 1: 1.5；Described disappears
Infusion is polyoxyethylene oxypropylene glycerol GPE20；The fungicide is the modified bi-quaternary ammonium salt of metronidazole.
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. reacting
30 parts of hydroxypropyl guars, 0.1 part of sodium hydroxide, 20 parts of water are added by above-mentioned weight proportion in kettle, at 25 DEG C (at 25 DEG C)
30min is continuously stirred, 3 parts of propylene oxide are added, is stirred, reflux, the reaction time is 3 hours, obtains reaction solution；2. 1. by step
Obtained reaction solution is warming up to 40 DEG C, and 0.15 part of catalyst sulfuric acid is added, and is slowly stirred 6 parts of ethyl alcohol of lower addition and 20 parts of lauryl alcohols
Mixed liquor, react 6.5 hours, obtain reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, it is added 5 part 7
Number white oil, 5 parts of No. 10 white oils, 1 part of OP-10 surfactant, 1.5 parts of AEO-9 surfactants, 1 part of defoaming agent polyoxyethylene
Oxypropylene glycerol GPE20,10 parts of mica powders, 1 part of fungicide, stir evenly, dry, are ground into a powder, as drilling fluid solid
Lubricant polysaccharid derivative (is ground into a powder, can cross 60 meshes to get solid lubricant for well drilling liquid polysaccharid derivative).
Embodiment 2: solid lubricant for well drilling liquid polysaccharid derivative of the present invention is the original matched by following weight
Made of material: 40 parts of hydroxypropyl guar, 4 parts of propylene oxide, 0.15 part of sodium hydroxide, 25 parts of lauryl alcohol, catalyst, that is, phosphoric acid 0.2
Part, 12 parts of white oil, 3 parts of surfactant, 2 parts of defoaming agent, 12 parts of mica powder, 2 parts of fungicide, 8 parts of ethyl alcohol, 10 parts of water；It is described
White oil be No. 7 white oils and No. 10 white oils combination, the weight ratio of No. 7 white oils and No. 10 white oils is 1: 2；The catalyst
Phosphoric acid is the phosphate aqueous solution that molar concentration is 0.1mol/L；The surfactant is OP-10 surfactant；Described
Defoaming agent is dimethyl silicone polymer；The fungicide is starch preservative DL-D401.
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. reacting
40 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 10 parts of water are added by above-mentioned weight proportion in kettle, are continuously stirred at 30 DEG C
4 parts of propylene oxide are added in 30min, stir, reflux, and the reaction time is 4 hours, obtain reaction solution；2. 1. step is obtained anti-
It answers liquid to be warming up to 42 DEG C, 0.2 part of catalyst phosphoric acid is added, be slowly stirred the lower mixed liquor that 8 parts of ethyl alcohol and 25 parts of lauryl alcohols is added,
Reaction 8 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, 4 parts of No. 7 white oils and 8 parts are added
No. 10 white oils, 3 parts of OP-10 surfactants, 2 parts of defoaming agent dimethyl silicone polymers, 12 parts of mica powders, 2 parts of fungicide, stirring
Uniformly, dry, it is ground into a powder, as solid lubricant for well drilling liquid polysaccharid derivative.
Embodiment 3: solid lubricant for well drilling liquid polysaccharid derivative of the present invention is the original matched by following weight
Made of material: 32 parts of hydroxypropyl guar, 3 parts of propylene oxide, 0.15 part of sodium hydroxide, 20 parts of lauryl alcohol, 0.15 part of catalyst, white
15 parts, 3 parts of surfactant, 2 parts of defoaming agent, 10 parts of mica powder, 2 parts of fungicide, 8 parts of ethyl alcohol, 18 parts of water of oil；The white oil
It is combined for No. 7 white oils with No. 10 white oils, the weight ratio of No. 7 white oils and No. 10 white oils is 1: 2；The catalyst be hydrochloric acid and
The combination of two kinds of raw materials of sulfuric acid, weight ratio 1: 1, the hydrochloric acid are the aqueous hydrochloric acid solution that molar concentration is 0.1mol/L,
The sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The surfactant be OP-10 surfactant,
The combination of two kinds of raw materials of AEO-9 surfactant, OP-10 surfactant, AEO-9 surfactant weight ratio be 1: 2；
The defoaming agent is polyoxyethylene oxypropylene glycerol GPE20；The fungicide is starch preservative DL-D401.
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. reacting
32 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 18 parts of water are added by above-mentioned weight proportion in kettle, are continuously stirred at 25 DEG C
3 parts of propylene oxide are added in 30min, stir, reflux, and the reaction time is 3.5 hours, obtain reaction solution；2. 1. step is obtained
Reaction solution is warming up to 40 DEG C, and 0.075 part of hydrochloric, 0.075 part of sulfuric acid is added, is slowly stirred lower addition 8 parts of ethyl alcohol and 20
The mixed liquor of part lauryl alcohol, reacts 7 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, add
Enter 5 parts of No. 7 white oils, 10 parts of No. 10 white oils, 1 part of OP-10 surfactant, 2 parts of AEO-9 surfactants, 2 parts of defoaming agent polyoxies
Ethylene oxypropylene glycerol GPE20,10 parts of mica powders, 2 parts of fungicide, stir evenly, dry, are ground into a powder, and as drilling fluid is used
Solid lubricant polysaccharid derivative.
Embodiment 4: solid lubricant for well drilling liquid polysaccharid derivative of the present invention is the original matched by following weight
Made of material: 35 parts of hydroxypropyl guar (powder), 3.5 parts of propylene oxide, 0.12 part of sodium hydroxide, 28 parts of lauryl alcohol, catalyst is
0.18 part of hydrochloric acid, 18 parts of white oil, 3.9 parts of surfactant, 0.15 part of defoaming agent, 16 parts of mica powder, 2 parts of fungicide, ethyl alcohol 9
Part, 22 parts of water；The white oil is the combination of two kinds of No. 7 white oils, No. 10 white oils raw materials, the weight of No. 7 white oils and No. 10 white oils
The ratio between be 1: 2；The surfactant uses the combination of two kinds of OP-10 surfactant, AEO-9 surfactant raw materials,
OP-10 surfactant, AEO-9 surfactant weight ratio be 1: 2；The hydrochloric is that molar concentration is
The aqueous hydrochloric acid solution of 0.1mol/L；The defoaming agent is dimethyl silicone polymer；The fungicide is that metronidazole is modified double
Quaternary ammonium salt.
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. reacting
35 parts of hydroxypropyl guars, 0.12 part of sodium hydroxide, 22 parts of water are added by above-mentioned weight proportion in kettle, are continuously stirred at 25 DEG C
3.5 parts of propylene oxide are added in 30min, stir, reflux, and the reaction time is 3.5 hours, obtain reaction solution；2. 1. step is obtained
Reaction solution be warming up to 40 DEG C, be added 0.18 part of hydrochloric, be slowly stirred the mixed of 9 parts of ethyl alcohol of lower addition and 28 parts of lauryl alcohols
Liquid is closed, reacts 7 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, addition 6 parts No. 7 is white
Oil, 12 parts of No. 10 white oils, 1.3 parts of OP-10 surfactants, 2.6 parts of AEO-9 surfactants, 0.15 part of poly- diformazan of defoaming agent
The modified bi-quaternary ammonium salts of radical siloxane, 16 parts of mica powders, 2 parts of fungicide metronidazoles, stir evenly, dry, are ground into a powder, (can be with
Cross 60 meshes) up to solid lubricant for well drilling liquid polysaccharid derivative.
Above-mentioned polyoxyethylene oxypropylene glycerol GPE20 is commercial goods, by grand vertical coin chemical industry preparation Co., Ltd, Xinxiang City
Production.Above-mentioned dimethyl silicone polymer is commercial goods, and the product of Shandong Xin Jie environmental protection technology Co., Ltd production can be used.
Above-mentioned fungicide is the modified bi-quaternary ammonium salt of metronidazole or starch preservative DL-D401, starch preservative DL-D401 factory
Family is moral oil blackeite work, is commercial goods, main component is 1,2- benzoisothiazolinone.Above-mentioned metronidazole is modified bi-quaternary ammonium salt
Commercial goods can also refer to following document and produce: " Xi'an Petroleum University's journal (natural science edition) ", the 05th phase in 2009,
Author Zhou Juan etc., one text of the synthesis of metronidazole bi-quaternary ammonium salt and bactericidal property research.
The following are test portions of the invention:
Table 1 be (more than) the solid lubricant polysaccharid derivative performance measurement result of each embodiment preparation.
Dosage (dosage) basis of solid lubricant for well drilling liquid polysaccharid derivative of the invention in drilling fluid (system)
Depending on actual drilling geology condition, the dosage of solid lubricant polysaccharid derivative is generally 1%~3% (weight percent),
The dosage of solid lubricant polysaccharid derivative is 2% in embodiment 1,2,3,4.
The solid lubricant polysaccharid derivative performance measurement result of each embodiment of table 1 preparation
The solid lubricant polysaccharid derivative of each embodiment of table 2 preparation performance measurement result after aging 16h at 190 DEG C
As shown in Table 1: the solid lubricant polysaccharid derivative of various embodiments of the present invention preparation can reach good performance
Effect.As shown in Table 2: the solid lubricant polysaccharid derivative of various embodiments of the present invention preparation also has good high temperature resistance,
It can use, while filter loss be influenced smaller under 190 DEG C of high temperature.
Solid lubricant polysaccharid derivative of the invention has the advantages that (1) is described solid compared with the prior art
Body lubricant polysaccharid derivative has good greasy property, advantageously reduces drilling well frictional resistance, is resistant to 190 DEG C of high temperature, and to brill
Apparent viscosity and the filter loss influence of well liquid are smaller, and compared with conventional lubricant, this product has better lubricity, high temperature drop
The comprehensive performances such as leak-off and salt-resistance, while having inhibition concurrently；(2) the solid lubricant polysaccharid derivative working condition is easy
Reach, property is stablized；(3) the solid lubricant polysaccharid derivative is nontoxic and pollution-free, easily biological-degradable, environmentally friendly；(4)
Compared with having relevant technology (compared with CN109054777A), manufacturing cost of the invention reduces 10% or more.
It is bored in conclusion the present invention solves big, poor, drilling rod of drilling fluid compatibility of drilling well frictional resistance etc. in present drilling process
Has problem easy to wear, it has good greasy property, while having good high temperature filtration reduction, salt-resistance, the solid
Lubricant polysaccharid derivative is nontoxic and pollution-free, and easily biological-degradable is environmentally friendly.
Claims (9)
1. a kind of solid lubricant for well drilling liquid polysaccharid derivative, it is characterised in that it is made of the raw material that following weight matches
: 30~40 parts of hydroxypropyl guar, 3~4 parts of propylene oxide, 0.1~0.15 part of sodium hydroxide, 20~30 parts of lauryl alcohol, catalysis
It 0.15~0.2 part of agent, 10~20 parts of white oil, 2~5 parts of surfactant, 0.1~2 part of defoaming agent, 10~20 parts of mica powder, kills
1~3 part of microbial inoculum, 6~10 parts of ethyl alcohol, 10~25 parts of water；
The white oil is the combination of one or both of No. 7 white oils, No. 10 white oils raw material, it is matched when two kinds of material combinations
It is arbitrary；The surfactant uses one or both of OP-10 surfactant, AEO-9 surfactant original
The combination of material, its proportion is arbitrary when two kinds of material combinations；The catalyst be one of sulfuric acid, hydrochloric acid, phosphoric acid or
The combination of several raw materials, its proportion is arbitrary when several material combinations；
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
Hydroxypropyl guar, sodium hydroxide, water is added by above-mentioned weight proportion, 25~30min is continuously stirred at 25~30 DEG C, ring is added
Ethylene Oxide stirs, reflux, and the reaction time is 3~4 hours, obtains reaction solution；2. 1. reaction solution that step is obtained is warming up to 40
~45 DEG C, catalyst is added, is slowly stirred the lower mixed liquor that ethyl alcohol and lauryl alcohol is added, reacts 6~8 hours, obtain reaction material
Liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, white oil, surfactant, defoaming agent, mica powder, sterilization is added
Agent stirs evenly, dry, is ground into a powder, as solid lubricant for well drilling liquid polysaccharid derivative.
2. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that above-mentioned catalyst
In, the sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The hydrochloric acid is that molar concentration is 0.1mol/L
Aqueous hydrochloric acid solution；The phosphoric acid is the phosphate aqueous solution that molar concentration is 0.1mol/L.
3. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that above-mentioned defoaming agent
For one of polyoxyethylene oxypropylene glycerol, dimethyl silicone polymer.
4. solid lubricant for well drilling liquid polysaccharid derivative according to claim 3, it is characterised in that when above-mentioned defoaming
When polyoxyethylene oxypropylene glycerol is selected in agent, polyoxyethylene oxypropylene glycerol uses polyoxyethylene oxypropylene glycerol GPE20.
5. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that above-mentioned fungicide
For the modified bi-quaternary ammonium salt of metronidazole or starch preservative DL-D401.
6. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that it is by following heavy
Made of the raw material for measuring proportion: 30 parts of hydroxypropyl guar, 3 parts of propylene oxide, 0.1 part of sodium hydroxide, 20 parts of lauryl alcohol, catalyst
That is 0.15 part of sulfuric acid, 10 parts of white oil, 2.5 parts of surfactant, 1 part of defoaming agent, 10 parts of mica powder, 1 part of fungicide, 6 parts of ethyl alcohol,
20 parts of water；The white oil is the combination of two kinds of raw materials of No. 7 white oils and No. 10 white oils, weight ratio 1: 1；The catalysis
Agent sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The surfactant is OP-10 surfactant, AEO-
The weight ratio of the combination of 9 two kinds of raw materials of surfactant, OP-10 surfactant and AEO-9 surfactant is 1: 1.5；
The defoaming agent is polyoxyethylene oxypropylene glycerol GPE20；The fungicide is the modified bi-quaternary ammonium salt of metronidazole；
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
30 parts of hydroxypropyl guars, 0.1 part of sodium hydroxide, 20 parts of water are added by above-mentioned weight proportion, continuously stir 30min at 25 DEG C,
3 parts of propylene oxide are added, stir, reflux, the reaction time is 3 hours, obtains reaction solution；2. 1. reaction solution liter that step is obtained
0.15 part of catalyst sulfuric acid is added to 40 DEG C in temperature, is slowly stirred the lower mixed liquor that 6 parts of ethyl alcohol and 20 parts of lauryl alcohols is added, reaction
6.5 hours, obtain reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, 5 parts of No. 7 white oils, 5 part 10 are added
Number white oil, 1 part of OP-10 surfactant, 1.5 parts of AEO-9 surfactants, 1 part of defoaming agent polyoxyethylene oxypropylene glycerol
GPE20,10 parts of mica powders, 1 part of fungicide, stir evenly, dry, are ground into a powder, as solid lubricant for well drilling liquid glycan
Derivative.
7. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that it is by following heavy
Made of the raw material for measuring proportion: 40 parts of hydroxypropyl guar, 4 parts of propylene oxide, 0.15 part of sodium hydroxide, 25 parts of lauryl alcohol, catalysis
0.2 part of agent, that is, phosphoric acid, 12 parts of white oil, 3 parts of surfactant, 2 parts of defoaming agent, 12 parts of mica powder, 2 parts of fungicide, 8 parts of ethyl alcohol,
10 parts of water；The white oil is the combination of No. 7 white oils and No. 10 white oils, and the weight ratio of No. 7 white oils and No. 10 white oils is 1: 2；
The catalyst phosphoric acid is the phosphate aqueous solution that molar concentration is 0.1mol/L；The surfactant is the surface OP-10
Activating agent；The defoaming agent is dimethyl silicone polymer；The fungicide is starch preservative DL-D401；
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
40 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 10 parts of water are added by above-mentioned weight proportion, continuously stir 30min at 30 DEG C,
4 parts of propylene oxide are added, stir, reflux, the reaction time is 4 hours, obtains reaction solution；2. 1. reaction solution liter that step is obtained
0.2 part of catalyst phosphoric acid is added to 42 DEG C in temperature, is slowly stirred the lower mixed liquor that 8 parts of ethyl alcohol and 25 parts of lauryl alcohols is added, reaction 8
Hour, obtain reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, 4 parts of No. 7 white oils and 8 parts No. 10 are added
White oil, 3 parts of OP-10 surfactants, 2 parts of defoaming agent dimethyl silicone polymers, 12 parts of mica powders, 2 parts of fungicide, stirring are equal
It is even, it is dry, it is ground into a powder, as solid lubricant for well drilling liquid polysaccharid derivative.
8. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that it is by following heavy
Made of the raw material for measuring proportion: 32 parts of hydroxypropyl guar, 3 parts of propylene oxide, 0.15 part of sodium hydroxide, 20 parts of lauryl alcohol, catalysis
0.15 part of agent, 15 parts of white oil, 3 parts of surfactant, 2 parts of defoaming agent, 10 parts of mica powder, 2 parts of fungicide, 8 parts of ethyl alcohol, water 18
Part；The white oil is that No. 7 white oils are combined with No. 10 white oils, and the weight ratio of No. 7 white oils and No. 10 white oils is 1: 2；Described
Catalyst is the combination of two kinds of raw materials of hydrochloric acid and sulfuric acid, and weight ratio 1: 1, the hydrochloric acid is that molar concentration is 0.1mol/L
Aqueous hydrochloric acid solution, the sulfuric acid is the aqueous sulfuric acid that molar concentration is 0.1mol/L；The surfactant is OP-
The combinations of two kinds of 10 surfactants, AEO-9 surfactant raw materials, OP-10 surfactant, AEO-9 surfactant
Weight ratio is 1: 2；The defoaming agent is polyoxyethylene oxypropylene glycerol GPE20；The fungicide is starch preservative
DL-D401；
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
32 parts of hydroxypropyl guars, 0.15 part of sodium hydroxide, 18 parts of water are added by above-mentioned weight proportion, continuously stir 30min at 25 DEG C,
3 parts of propylene oxide are added, stir, reflux, the reaction time is 3.5 hours, obtains reaction solution；2. 1. reaction solution that step is obtained
40 DEG C are warming up to, 0.075 part of hydrochloric, 0.075 part of sulfuric acid is added, is slowly stirred 8 parts of ethyl alcohol of lower addition and 20 part 12
The mixed liquor of alcohol reacts 7 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, it is added 5 part 7
Number white oil, 10 parts of No. 10 white oils, 1 part of OP-10 surfactant, 2 parts of AEO-9 surfactants, 2 parts of defoaming agent polyoxyethylene oxygen
Propylene glycerol GPE20,10 parts of mica powders, 2 parts of fungicide, stir evenly, dry, are ground into a powder, as drilling fluid solid moistens
Lubrication prescription polysaccharid derivative.
9. solid lubricant for well drilling liquid polysaccharid derivative according to claim 1, it is characterised in that it is by following heavy
Made of the raw material for measuring proportion: 35 parts of hydroxypropyl guar, 3.5 parts of propylene oxide, 0.12 part of sodium hydroxide, 28 parts of lauryl alcohol, urging
0.18 part of agent, that is, hydrochloric acid, 18 parts of white oil, 3.9 parts of surfactant, 0.15 part of defoaming agent, 16 parts of mica powder, 2 parts of fungicide,
9 parts of ethyl alcohol, 22 parts of water；The white oil is the combination of two kinds of No. 7 white oils, No. 10 white oils raw materials, No. 7 white oils and No. 10 white oils
Weight ratio is 1: 2；The surfactant uses the group of two kinds of OP-10 surfactant, AEO-9 surfactant raw materials
Close, OP-10 surfactant, AEO-9 surfactant weight ratio be 1: 2；The hydrochloric is molar concentration
For the aqueous hydrochloric acid solution of 0.1mol/L；The defoaming agent is dimethyl silicone polymer；The fungicide is modified for metronidazole
Bi-quaternary ammonium salt；
The preparation method of the solid lubricant for well drilling liquid polysaccharid derivative comprises the technical steps that: 1. in reaction kettle
35 parts of hydroxypropyl guars, 0.12 part of sodium hydroxide, 22 parts of water are added by above-mentioned weight proportion, continuously stir 30min at 25 DEG C,
3.5 parts of propylene oxide are added, stir, reflux, the reaction time is 3.5 hours, obtains reaction solution；2. 1. reaction that step is obtained
Liquid is warming up to 40 DEG C, is added 0.18 part of hydrochloric, is slowly stirred the lower mixed liquor that 9 parts of ethyl alcohol and 28 parts of lauryl alcohols is added,
Reaction 7 hours, obtains reaction material liquid；3. 2. reaction material liquid that step is obtained is cooled to room temperature, 6 parts of No. 7 white oils, 12 parts are added
No. 10 white oils, 1.3 parts of OP-10 surfactants, 2.6 parts of AEO-9 surfactants, 0.15 part of defoaming agent polydimethylsiloxanes
Alkane, 16 parts of mica powders, the modified bi-quaternary ammonium salt of 2 parts of fungicide metronidazoles, stir evenly, dry, are ground into a powder, as drilling fluid is used
Solid lubricant polysaccharid derivative.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717622A (en) * | 2009-11-30 | 2010-06-02 | 北京奥凯立科技发展股份有限公司 | Lubricating inhibitor for drilling fluid and preparation method thereof and drilling fluid containing lubricating inhibitor for drilling fluid |
| US20170260444A1 (en) * | 2013-10-23 | 2017-09-14 | Baker Hughes Incorporated | Well treatment fluids containing biodegradable zirconium crosslinker and methods of using the same |
| CN109054777A (en) * | 2018-08-17 | 2018-12-21 | 石家庄华莱鼎盛科技有限公司 | Solid lubricant for well drilling liquid polysaccharid derivative and preparation method thereof |
| CN109370544A (en) * | 2018-10-21 | 2019-02-22 | 石家庄华莱鼎盛科技有限公司 | Drilling fluid inhibition lubricant ether polymer and preparation method thereof |
-
2019
- 2019-05-25 CN CN201910442742.2A patent/CN110105929B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717622A (en) * | 2009-11-30 | 2010-06-02 | 北京奥凯立科技发展股份有限公司 | Lubricating inhibitor for drilling fluid and preparation method thereof and drilling fluid containing lubricating inhibitor for drilling fluid |
| US20170260444A1 (en) * | 2013-10-23 | 2017-09-14 | Baker Hughes Incorporated | Well treatment fluids containing biodegradable zirconium crosslinker and methods of using the same |
| CN109054777A (en) * | 2018-08-17 | 2018-12-21 | 石家庄华莱鼎盛科技有限公司 | Solid lubricant for well drilling liquid polysaccharid derivative and preparation method thereof |
| CN109370544A (en) * | 2018-10-21 | 2019-02-22 | 石家庄华莱鼎盛科技有限公司 | Drilling fluid inhibition lubricant ether polymer and preparation method thereof |
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