CN111039805A - Environment-friendly lubricant and continuous preparation method thereof - Google Patents

Environment-friendly lubricant and continuous preparation method thereof Download PDF

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Publication number
CN111039805A
CN111039805A CN201811190585.2A CN201811190585A CN111039805A CN 111039805 A CN111039805 A CN 111039805A CN 201811190585 A CN201811190585 A CN 201811190585A CN 111039805 A CN111039805 A CN 111039805A
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reaction
lubricant
soybean oil
epoxidized soybean
reaction module
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Inventor
储政
袁俊秀
江瑞晶
封心领
逯贵广
徐冬梅
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • 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
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Lubricants (AREA)

Abstract

The invention relates to an environment-friendly lubricant and a continuous preparation method thereof, and the preparation method of the environment-friendly efficient drilling lubricant comprises the following steps: respectively enabling raw materials of epoxidized soybean oil and amine substances to enter a microchannel reactor through two inlets of the microchannel reactor, and controlling the mass ratio of the epoxidized soybean oil to the amine substances to be (1-3) by regulating and controlling the volume flow of the raw materials: 1, controlling the reaction temperature of the reaction module to be 120-200 ℃, keeping the reaction materials in the reaction module for 5-50 min, and cooling the reaction liquid to room temperature after the reaction is finished to obtain a finished lubricant.

Description

Environment-friendly lubricant and continuous preparation method thereof
Technical Field
The invention relates to an environment-friendly lubricant and a continuous preparation method thereof, and the lubricant prepared by the invention is applied to the technical field of drilling engineering.
Background
Along with the development of oil and gas exploration and development towards deep strata, shale gas strata and marine strata, deep wells, highly deviated wells and large-displacement horizontal wells are rapidly increased, the risk of sticking stuck drill bits in the drilling process is increased due to the operation mode of the horizontal wells, the requirement on the lubricating property of the drilling fluid is increased, meanwhile, along with the implementation of a new environment-friendly method, the requirement on the environmental protection property of drilling construction is increased, the drilling auxiliary agent required to be used is required to be environment-friendly, and the conventional liquid water-based lubricant for oil fields is mainly divided into mineral oil and vegetable oil lubricants.
Chinese patent 200810055861.4 discloses a water-based lubricant for drilling fluid and a preparation method thereof, wherein the formula of the lubricant is as follows: 100-300 parts of water, 10-30 parts of emulsifier, 50-300 parts of castor oil, 50-400 parts of white oil, 50-600 parts of oleic soap and 50-200 parts of defoaming agent.
Chinese patent 200510106571.4 discloses a low-fluorescence lubricant for drilling fluid and a production method thereof. Adding 50-90 parts of aviation kerosene and 15-75 parts of industrial white oil into a reaction kettle, heating to 70-90 ℃ by using a water jacket furnace, stirring for 30-60 minutes, adding 0.5-2.5 parts of sulfur powder, stirring, continuously heating to 90-100 ℃, adding 3.5-8.5 parts of oleic acid, stirring for 30-60 minutes, cooling to 70-80 ℃, adding 3.5-8.5 parts of polyoxyethylene ether and 0.5-2.5 parts of SP-80, and stirring for 30-60 minutes to obtain the low-fluorescence lubricant for the drilling fluid.
Chinese patent 200710158398.1 discloses a method for preparing a high-temperature-resistant lubricant for drilling fluid by using animal and vegetable oil. 50-70 parts of waste oil and fat, 3-10 parts of ethanolamine and 5-20 parts of diethylene glycol are subjected to esterification reaction, 1-3 parts of sulfur is used for vulcanization reaction, 2-5 parts of oil-soluble resin and 10-30 parts of graphite powder are added into the reaction product, and the mixture is mixed and stirred uniformly to obtain the high-temperature resistant lubricant for the drilling fluid.
The preparation of drilling fluid lubricants from leftovers from the grease industry has become a trend. The leftovers in the grease industry mainly comprise: the waste material from the production of glycerin and synthetic glycerin, the by-product of castor oil to prepare sebacic acid, the waste material from lecithin production, cottonseed oil soapstock, animal and vegetable fat residual oil, forest oil and wild vegetable oil leftovers, rapeseed oil leftovers and refined vegetable oil (salad oil) active waste carclazyte.
Some of the lubricants are mineral oil which has high toxicity and is not easy to biodegrade and is easy to harm the environment after being retained in the environment for a long time; some adopt animal and vegetable oil or animal and vegetable oil grease lubricant, the animal and vegetable oil or animal and vegetable oil contains oleic acid, linoleic acid, oleic acid, linoleic acid unsaturated bond lead to the product fluorescence level high, oleic acid, linoleic acid water-solubility are poor at the same time, disperse unevenly in the slurry, difficult to adsorb on the clay mineral surface, lead to the poor lubricating property.
At present, most of lubricants for drilling fluid are compounded products and are prepared by stirring in a reaction kettle, and the technology has the following defects: (1) the intermittent reaction needs auxiliary time, the utilization rate of equipment is not high, and automatic control is not easy to realize; (2) the stirring equipment has high energy consumption, high operation cost in industrial production, undesirable mass transfer of stirring reaction and low conversion rate and yield; (3) reaction products cannot be discharged in time, which is not favorable for forward reaction. Microchannel reaction technology has many inherent and unique advantages: high mass transfer rate; fast direct amplification (modular structure, parallel amplification); intrinsic safety and process control; the process is continuous and highly integrated. The lubricant production process disclosed by the invention is a liquid-liquid reaction, the mixing degree of two phases is a key for influencing the reaction, and the microchannel reactor can realize rapid and efficient mixing.
Disclosure of Invention
The invention aims to solve the problems of high friction resistance in the construction process of deep wells, highly deviated wells and large-displacement horizontal wells under new conditions, insufficient lubricity, high fluorescence level, poor environmental protection performance and the like of the conventional lubricant for the water-based drilling fluid, and provides a lubricant with good environmental protection performance and excellent lubricating performance to solve the problems.
The purpose of the invention is realized by the following technical scheme: the environment-friendly lubricant is characterized by being prepared from epoxidized soybean oil and amine substances by a continuous method, wherein the mass ratio of the epoxidized soybean oil to the amine substances is (1-3): 1.
generally, the mass ratio of the epoxidized soybean oil to the amine substances is (1-2): 1.
the amine substance is as follows: one or a mixture of more of ethanolamine, diethanolamine and triethanolamine.
The invention relates to a continuous preparation method of an environment-friendly lubricant, which comprises the following steps: raw materials of epoxidized soybean oil and amine substances respectively enter the microchannel reactor through two inlets of the microchannel reactor, the mass ratio of the epoxidized soybean oil and the amine substances is controlled by regulating and controlling the volume flow of the raw materials, the reaction temperature of the reaction module is controlled to be 120-200 ℃, the residence time of the reaction materials in the reaction module is 5-50 min, and after the reaction is finished, the reaction liquid is cooled to room temperature to obtain a finished lubricant.
The reaction module structure of the microchannel reactor is a direct-flow channel structure or an enhanced mixed heart-shaped channel structure.
The reaction temperature of the reaction module is 160-190 ℃.
The residence time of the materials in the reaction module is 5-30 min.
The environment-friendly lubricant is applied to a water-based drilling fluid system.
The lubricant has excellent lubricity and antifriction and resistance reduction performance, can effectively improve the lubricity of drilling fluid, prevent the problems of dragging pressure, sticking and the like, and improve the drilling speed; meanwhile, the environment-friendly performance is good, no biotoxicity exists, and the environment-friendly material is easy to degrade; no fluorescence, can be used for exploratory well drilling, and has wide application range. The lubricant is synthesized by adopting the microchannel reaction technology, the mass transfer rate of the microchannel reactor is high, the reaction process is safe and controllable, the continuous production is realized, the amplification effect is avoided, and the three wastes are not generated in the reaction process.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Example 1
Under the condition of normal temperature, the epoxidized soybean oil and the ethanolamine are injected into a microchannel reactor through a metering pump to react, the mass ratio of the epoxidized soybean oil to the ethanolamine is controlled to be 1:1, the reaction temperature of a reaction module is 180 ℃, and the residence time of the reaction module is 15 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 1#。
Example 2
Under the condition of normal temperature, epoxy soybean oil and triethanolamine are injected into a micro-channel reactor through a metering pump to react, the mass ratio of the epoxy soybean oil to the triethanolamine is controlled to be 1:1, the reaction temperature of a reaction module is 160 ℃, and the residence time of the reaction module is 20 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 2#。
Example 3
Under the condition of normal temperature, epoxy soybean oil and diethanol amine are injected into a microchannel reactor through a metering pump to react, the mass ratio of the epoxy soybean oil to the diethanol amine is controlled to be 2:1, the reaction temperature of a reaction module is 180 ℃, and the residence time of the reaction module is 18 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 3#。
Example 4
Under the condition of normal temperature, epoxy soybean oil and ethanolamine are injected into a microchannel reactor through a metering pump to react, the mass ratio of the epoxy soybean oil to the diethanolamine is controlled to be 1:1, the reaction temperature of a reaction module is 200 ℃, and the residence time of the reaction module is 5 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 4#。
Example 5
Under the condition of normal temperature, epoxy soybean oil and triethanolamine are injected into a micro-channel reactor through a metering pump for reaction, the mass ratio of the epoxy soybean oil to the triethanolamine is controlled to be 3:1, and the reaction temperature of a reaction module is controlled to be 3The residence time of the reaction module was 20min at 190 ℃. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 5#。
Example 6
Under the condition of normal temperature, the mixed solution of epoxidized soybean oil, diethanol and triethanolamine is injected into a micro-channel reactor through a metering pump to react, the mass ratio of the epoxidized soybean oil to the mixed solution of the diethanol and the triethanolamine is controlled to be 1.5:1, the reaction temperature of a reaction module is 170 ℃, and the residence time of the reaction module is 20 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 5#。
Example 7
Under the condition of normal temperature, epoxy soybean oil and diethanol amine are injected into a microchannel reactor through a metering pump to react, the mass ratio of the epoxy soybean oil to the diethanol amine is controlled to be 1.5:1, the reaction temperature of a reaction module is 120 ℃, and the residence time of the reaction module is 50 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 6#。
Example 8
Under the condition of normal temperature, the mixed solution of epoxidized soybean oil and triethanolamine is injected into a microchannel reactor through a metering pump for reaction, the mass ratio of the mixed solution of epoxidized soybean oil and triethanolamine is controlled to be 1:1, the reaction temperature of a reaction module is 190 ℃, and the residence time of the reaction module is 18 min. The reactant continuously flows out of the reactor and is collected with the collector at normal temperature, and the product is the lubricant 7#。
Example 9
And (3) testing the reduction rate of the lubrication coefficient:
preparing four parts of base slurry, adding 300mL of distilled water, 0.42g of anhydrous sodium carbonate and 12.0g of sodium bentonite for drilling fluid test into each part, stirring for 20min on a high-speed stirrer, stopping twice in the stirring process, scraping the bentonite adhered to a stirring cup by using a glass rod, and sealing and maintaining for 24h at room temperature. Two of the base slurries were removed and 6g of lubricant sample was added, and four portions were stirred high for 5 min. The lubrication coefficients of the base slurry and the sample slurry are respectively measured on an E-P extreme pressure lubrication instrument, the measuring method is according to a SY/T6094 lubricant evaluation program for drilling fluid (a torque arm applies 150psi pressure, and keeps the rotating speed at 60r/min), and the reduction rate of the lubrication coefficient is calculated by using a formula (1).
Figure RE-DEST_PATH_IMAGE001
×100------------- （1）
In the formula:
η -reduction of lubrication coefficient,%;
w0-the lubricity coefficient of the base slurry;
w1-the lubricity coefficient of the base slurry after the addition of the friction reducing agent.
The test results are shown in Table 1.
TABLE 1 lubrication coefficient reduction test results
Sample (I) Reduction of lubricity coefficient/%)
Example 1# 87.6
Example 2# 88.4
Example 3# 91.4
Example 4# 92.4
Example 5# 89.6
Example 6# 87.7
Example 7# 88.6
Example 8# 91.3
As can be seen from Table 2, when 2% of the lubricant is added to the base slurry, the reduction rate of the lubrication coefficient is about 90%, which indicates that the lubrication performance of the lubricant is good.
Example 10
Evaluation of rheological Properties in Polymer well slurries
The rheology of the slurry was tested before and after 2% lubricant addition using a polymer slurry. The test results are shown in Table 2.
TABLE 2 drilling fluid Performance test
Figure RE-RE-DEST_PATH_IMAGE002
The test result shows that the lubricant basically has no influence on the rheological property of the drilling fluid system, can obviously improve the lubricating property of the well slurry and has better compatibility.
Example 11
Biotoxicity testing
Experimental methods test Standard reference GB/T15441-1995. Oil water fusion component (WAF) -luminescent bacteria method.
Preparing a series of mass concentrations (g/L) of the lubricant by using sterilized 3% NaCl, placing the lubricant in a beaker, stirring for 24 hours by using a magnetic stirrer at the stirring speed of 900r/min and the temperature of 25 ℃, and standing for 1 hour.
Preparing reference poison ZnSO at the same time4Concentration gradients (and each concentration contained 3% NaCl). Zn with ZnSO4 as reference poison2+When the concentration is 4.8 mg/L, the 15min luminescence inhibition rate is 54.4%; meanwhile, the light inhibition rate of 3% NaCl in 15min is 4.1%, which shows that the light attenuation and the response to poison of the luminous bacteria meet the requirements. Toxicity testing was performed on the 3% lubricant solution and the results are shown in table 3.
TABLE 3 Lubricant biotoxicity testing
Sample (I) Luminescent bacterium EC50(mg/L)
Example 1# 21.3×104
Example 3# 25.4×104
Example 7# 22.7×104

Claims (8)

1. The environment-friendly lubricant is characterized by being prepared from epoxidized soybean oil and amine substances by a continuous method, wherein the mass ratio of the epoxidized soybean oil to the amine substances is (1-3): 1.
2. the environmentally friendly lubricant according to claim 1, wherein the epoxidized soybean oil and the amine-based substance are present in a mass ratio of (1-2): 1.
3. the environmentally friendly lubricant according to claim 1, wherein the amine is: one or a mixture of more of ethanolamine, diethanolamine and triethanolamine.
4. A continuous process for preparing the environmentally friendly lubricant of claim 1, comprising the steps of: raw materials of epoxidized soybean oil and amine substances respectively enter the microchannel reactor through two inlets of the microchannel reactor, the mass ratio of the epoxidized soybean oil and the amine substances is controlled by regulating and controlling the volume flow of the raw materials, the reaction temperature of the reaction module is controlled to be 120-200 ℃, the residence time of the reaction materials in the reaction module is 5-50 min, and after the reaction is finished, the reaction liquid is cooled to room temperature to obtain a finished lubricant.
5. The method according to claim 4, wherein the microchannel reactor has a reaction module structure of a flow-through type channel structure or a reinforced mixed core type channel structure.
6. The method of claim 4, wherein the reaction temperature of the reaction module is 160 ℃ to 190 ℃.
7. The method of claim 2, wherein the residence time of the material in the reaction module is 5-30 min.
8. The environmentally friendly lubricant of claim 1, wherein the lubricant is used in a water based drilling fluid system.
CN201811190585.2A 2018-10-12 2018-10-12 Environment-friendly lubricant and continuous preparation method thereof Pending CN111039805A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090099861A (en) * 2008-03-18 2009-09-23 건국대학교 산학협력단 Polyaminol and adhesive synthesized therefrom
CN103396342A (en) * 2013-08-08 2013-11-20 江苏卡特新能源有限公司 Preparation of modified polyfunctional acrylate photo polymerization monomers based on epoxidized soybean oil
CN104419387A (en) * 2013-08-20 2015-03-18 中国石油化工股份有限公司 Method for preparing water-based drilling fluid lubricant with micro-channel reactor
CN104962397A (en) * 2015-03-20 2015-10-07 南京工业大学 Method for producing biodiesel through ester interchange in continuous-flow micro-channel reactor
CN108610616A (en) * 2018-05-03 2018-10-02 佛山九陌科技信息咨询有限公司 A kind of preparation method of shock-resistant degradable bubble chamber film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090099861A (en) * 2008-03-18 2009-09-23 건국대학교 산학협력단 Polyaminol and adhesive synthesized therefrom
CN103396342A (en) * 2013-08-08 2013-11-20 江苏卡特新能源有限公司 Preparation of modified polyfunctional acrylate photo polymerization monomers based on epoxidized soybean oil
CN104419387A (en) * 2013-08-20 2015-03-18 中国石油化工股份有限公司 Method for preparing water-based drilling fluid lubricant with micro-channel reactor
CN104962397A (en) * 2015-03-20 2015-10-07 南京工业大学 Method for producing biodiesel through ester interchange in continuous-flow micro-channel reactor
CN108610616A (en) * 2018-05-03 2018-10-02 佛山九陌科技信息咨询有限公司 A kind of preparation method of shock-resistant degradable bubble chamber film

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黄显慈: "制取羟基脂肪酸衍生物的新方法", 《四川化工》 *

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