CN112094991A - A kind of environmental protection high temperature isothermal graded quenching oil and preparation method thereof - Google Patents

Abstract

The invention provides environment-friendly high-temperature isothermal grading quenching oil which is composed of 150BS bright stock, a cooling accelerant, an antioxidant, a brightener, an antirust agent and an antifoaming agent. The invention also provides a preparation method of the environment-friendly high-temperature isothermal grading quenching oil. The most remarkable characteristics of the invention are that the high-temperature cooling is fast and the low-temperature cooling is gentle; the flash point is high, the service temperature is high, the thermal oxidation resistance is good, and the service life is long; the brightness and the rust resistance are excellent; meets the technical index requirements of the isothermal graded quenching oil No. 2 of SH/T0564-93 heat treatment oil in the petrochemical industry standard in China. In addition, the invention has simple production and preparation process, environment-friendly product and stable quality.

Description

A kind of environmental protection high temperature isothermal graded quenching oil and preparation method thereof

technical field

The invention belongs to the field of petrochemical industry, and relates to a quenching oil, in particular to an environment-friendly high-temperature isothermal graded quenching oil and a preparation method thereof.

Background technique

With the progress of the times, the current society has put forward higher requirements for mechanical metal materials-not only high strength and hardness, but also good comprehensive mechanical properties are required to ensure that the cost does not increase significantly. Quenching is an important process in the processing of mechanical manufacturing materials. The so-called quenching is to heat the steel to a temperature above the austenite transformation point, keep it for a certain period of time, and then cool it at an appropriate speed to obtain martensite and (or) bainite. Body tissue heat treatment process. The purpose of quenching is to improve the hardness, strength, wear resistance, toughness, fatigue strength and corrosion resistance of steel, so that the workpiece can obtain good comprehensive performance. It is necessary to make austenite with low strength and poor thermal conductivity in the steel to transform into martensite and bainite with high strength, hardness and good toughness during cooling, so as to avoid becoming tough and plastic, strength and hardness. Insufficient pearlite, the cooling rate must be greater than the critical cooling rate of the steel to ensure that the entire workpiece is transformed into martensite and bainite, and a quenching medium with sufficient cooling capacity needs to be selected. However, the cooling rate is large, and the internal stress caused by uneven thermal expansion and contraction inside the workpiece may cause deformation or cracking of the workpiece. Therefore, the above two contradictory factors should be considered, and the cooling method and quenching medium should be reasonably selected.

The continuous cooling method means that the steel is continuously cooled to room temperature in the high temperature austenite state. The isothermal cooling method refers to the rapid cooling of the steel from the austenitic state to a temperature below the critical temperature, causing it to undergo a constant temperature transformation, and then cooling down; the latter has a certain cooling capacity, small deformation, good performance in terms of performance. The requirements of the three aspects of brightness have overcome the shortcomings of the former that the deformation is not easy to control, and even quenched and cracked, and it has gradually become the general trend of the current cooling method.

The quenching and cooling process can be divided into three stages. The first stage is the steam film stage. After the workpiece is immersed in the quenching medium, the quenching medium will rapidly vaporize on the surface of the hot workpiece. At this time, the quenched workpiece will be wrapped by the steam film of the quenching medium. Poor heat dissipation and slow cooling; the second stage is the boiling stage. After the vapor film of the quenching medium is broken, the quenching workpiece is in direct contact with the surrounding quenching medium to conduct intense heat exchange. This stage has the fastest cooling speed; the third stage is convection. At this stage, the temperature of the workpiece surface is reduced to below the boiling point temperature of the quenching medium, the heat of the quenching workpiece is mainly taken away by the convection of the quenching medium, and the cooling rate is the slowest. The temperature difference is important.

There are many kinds of quenching media used in my country, and the common ones are quenching oil, water-based quenching medium and molten salt. The cooling rate of the water-based quenching medium is too fast, which is easy to cause large dimensional changes or even cracking of the quenched parts, and the water is easy to evaporate. , it will cause damage to the components of the equipment, destroy the quenching atmosphere, damage the heat treatment equipment and even cause catastrophic accidents, so it is difficult to apply it to austempering cooling. In addition, water-based quenching medium, like molten salt substances, is easy to corrode workpieces and equipment, and the working environment is poor. The surface tension of the quenching oil is large, and the steam film is easily broken in the initial stage of quenching, which can obtain better cooling capacity; in the boiling and convection stages, the heat dissipation of the quenching oil is moderate and uniform, which can obtain better deformation control than water, and if The base oil viscosity is selected reasonably, the cooling additive ratio is appropriate, and the deep hardening ability can be compared with the water-based quenching medium. Therefore, quenching oil, as a quenching medium, is currently used in the largest amount and plays an important role in the heat treatment of steel.

Isothermal graded quenching is to heat the workpiece to austenitize, immerse it in a quenching medium at a temperature between the bainite transformation temperature and the martensitic transformation temperature, and then keep it for an appropriate time, until the temperature inside and outside the workpiece reaches the temperature of the quenching medium. After that, continue to cool to room temperature to obtain a bainite + martensite integrated structure with high strength and hardness, appropriate toughness, strong wear resistance and corrosion resistance, and good processing performance, and the quenching process of the workpiece to minimize deformation and cracking. Isothermal graded quenching is mainly used for the quenching of thin-walled, slender, concave-hole, and hollow ferrule precision components that require stricter dimensional changes. Common quenched parts include bearing rings, gears, clutch diaphragms, etc.

These requirements of isothermal graded quenching require the quenching oil to be used at a higher temperature, with a higher high-temperature cooling rate and a lower low-temperature cooling rate to ensure a suitable bainite/martensite ratio. my country's petrochemical industry standard SH/T 0564-93 "Heat Treatment Oil" has made specific requirements for the technical indicators of isothermal graded quenching oil, among which the cooling performance is the assessment of "characteristic temperature" and "cooling time of 800 ~ 400 ℃". They are obtained by drawing the cooling curve shown in Figure 1 in accordance with my country's petrochemical industry standard SH/T 0220 "Determination of Cooling Performance of Heat Treatment Oil". The intersection point is parallel to the X-axis as the temperature corresponding to a point on the curve where the lead intersects; the cooling time at 800 to 400°C is the time for the parallel line to intersect at a point on the curve at 400°C on the Y-axis (see Figure 1).

The characteristic temperature of quenching oil is the temperature at which the quenching oil vapor film on the surface of the workpiece breaks during the cooling process, that is, the temperature at which boiling starts. The higher the characteristic temperature and the shorter the cooling time, the better the high temperature cooling performance of the quenching oil. At the nose tip of the C curve (see Figure 2), austenite is the most unstable, and it is easier to transform into other organizational forms such as pearlite. Therefore, the characteristic temperature of the quenching oil required by the steel should be higher than the temperature of the nose tip of the isothermal transformation curve (C curve) of the steel (see Figure 2). The second evaluation parameter of cooling performance is the cooling time of 800-400℃, which is the main index to evaluate whether the quenching oil can make the workpiece obtain sufficient critical cooling rate, and also represents the average cooling rate in this interval. The ideal cooling curve of isothermal graded quenching oil is rapid cooling in the range of 650-400℃, bypassing the nose tip of the C curve, the slope of the cooling curve decreases below 400℃, and the cooling rate gradually tends to be gentle until it reaches the operating temperature of the quenching oil ( See Figure 2).

Quenching oil should also meet the following performance requirements:

(1) High flash point and ignition point, not easy to volatilize, inhibit the generation of oil fume during quenching, reduce pollution, improve the working environment, and reduce the possibility of fire. The flash point is a safety performance indicator, which should be 60-80°C higher than the operating temperature of the oil.

(2) Does not corrode the workpiece.

(3) It has strong thermal oxidation resistance and prolongs the service life of quenching oil. If the quenching oil is not heat resistant, organic chain scission and degradation with volatile by-products will occur, resulting in a lower flash point and a fire hazard. Oxidation of quenching oil will form oil stains and carbon deposits. One of the biggest problems in the use of quenching oil is the formation of oil stains. Oil stains may cause the filter system to block and deposit on the surface of the workpiece, resulting in uneven heat transfer, increased local overheating and cracking risk of distortion. If the amount of oil pollution reaches 0.2%, the workpiece will be rusted. In a sense, the carbon residue index can reflect the formation tendency of sludge.

(4) The use temperature of quenching oil is high, and it is easy to deposit asphalt and colloid on the surface of the workpiece, so the quenching oil requires certain cleaning and dispersing properties to maintain a better bright appearance of the workpiece.

(5) From the perspective of environmental protection, the content of aromatic hydrocarbons in oil products should be as little as possible.

The Chinese patent with publication number CN1078489A discloses a classification quenching oil, the classification quenching oil includes the following components: in parts by mass, 100 parts of 650SN neutral oil, 0.5 part of sodium petroleum sulfonate, 0.1 part of random polypropylene parts, 0.04 part of dodecenylsuccinic acid, 0.5 part of sorbitol monooleate, 0.6 part of 2,6-di-tert-butyl-p-cresol, 4,4-methylene-2,6-di-tert-butyl 0.4 part of base phenol has the problems of low flash point, poor thermal oxidation stability, low characteristic temperature, long cooling time at 800-400°C and too fast low temperature cooling rate.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a kind of environment-friendly high temperature isothermal graded quenching oil and preparation method thereof, and described this kind of environment-friendly high temperature isothermal graded quenching oil and preparation method thereof should solve the problem of low flash point, low heat and high temperature of graded quenching oil in the prior art. The technical problems of poor oxidation stability, low characteristic temperature, long cooling time at 800-400°C and too fast low temperature cooling rate.

The invention provides an environment-friendly high-temperature isothermal graded quenching oil, which is composed of 150BS bright oil, a cooling agent, an antioxidant, a brightener, a rust inhibitor and an anti-foaming agent. In the environment-friendly high-temperature isothermal graded quenching oil, The weight percentage of the 150BS bright oil is 89 to 93%, the weight percentage of the cooling agent is 3 to 8%, the weight percentage of the antioxidant is 1 to 2%, and the brightener is 1 to 2%. The weight percentage of the rust inhibitor is 0.3-1%, the weight percentage of the rust inhibitor is 1-2%, and the weight percentage of the anti-foaming agent is 0.01-0.03%.

Further, the 150BS bright stock is "HVI base oil" in the enterprise standard Q/SY44-2009 "General Lubricant Base Oil" of China National Petroleum Corporation.

Further, the cooling agent is any one or a combination of two or more of maleic acid-ethylene-propylene terpolymer, polyisobutylene or polyisobutylene bis-succinimide. .

Further, the antioxidant is any one of 2,6-di-tert-butyl-p-cresol, dinonyldiphenylamine, N-phenyl-α-naphthylamine or thiodipropionate or combination of two or more.

Further, the brightening agent is any one or a combination of two or more of imidazoline oleate, sorbitan monooleate or methyl terpene resin.

Further, the rust inhibitor is any one or a mixture of two or more of dodecenylsuccinic acid, barium petroleum sulfonate or barium dinonylnaphthalene sulfonate.

Further, the anti-foaming agent is any one or a combination of two or more of dimethicone oil with a viscosity of 100 cst at 25° C., an acrylate and an ether copolymer.

The present invention also provides a method for preparing the environment-friendly high-temperature isothermal graded quenching oil: firstly weigh 150BS bright oil, a cooling agent, an antioxidant, a brightening agent, a rust inhibitor and an anti-foaming agent according to the mass percentage, and then Add 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor and anti-foaming agent in sequence to the reaction vessel, stir at 50-70°C and normal pressure at a speed of 50r/min for 2-5 hours, wait for After all the various materials are dissolved, filter into the finished product tank to obtain the environmentally friendly high temperature isothermal graded quenching oil.

Beneficial effects of the present invention:

1. The selected 150BS bright oil base oil has high flash point, high operating temperature, not easy to evaporate loss, environmental protection and safety.

2. 150BS bright oil has high viscosity, slow cooling rate at low temperature, and minimizes workpiece deformation and cracking.

3. The surface tension of 150BS bright oil is large, coupled with the piercing effect of the coolant on the vapor film, the vapor film is easily broken, the characteristic temperature is high, and the cooling speed in the high temperature area is fast.

4. 150BS bright oil has strong sensitivity to additives, and can be well blended and synergized with various additives to give full play to the effect of additives.

5. 150BS bright oil and high-efficiency antioxidant synergize, high temperature thermal oxidation stability, long oil life.

6. 150BS bright oil is compounded with a unique brightening agent, which shows the excellent ability to dissolve and clean sludge and carbon deposits and effectively prevent their formation.

7. The specially added rust inhibitor provides good rust protection for workpieces and equipment.

8. The added defoamer can inhibit the generation of oil foam and make the foam disappear quickly to ensure the quenching effect.

9. The production and preparation process is simple, the product is environmentally friendly, and the quality is stable.

Compared with the prior art, the technical effect of the present invention is positive and obvious. The environment-friendly high-temperature isothermal graded quenching oil of the invention has fast cooling at high temperature and gentle cooling at low temperature; high flash point, high service temperature, good thermal oxidation resistance and long service life; excellent brightness and anti-rust performance; T 0564-93 "Heat Treatment Oil" No. 2 isothermal graded quenching oil technical index requirements.

Description of drawings

Figure 1 shows the cooling curve.

Figure 2 shows the relationship between the cooling curve of the quenching oil and the isothermal transformation C curve of the steel.

FIG. 3 shows the cooling curves of examples of the present invention and comparative examples.

Detailed ways

Example 1

The invention provides an environment-friendly high-temperature isothermal graded quenching oil, which is composed of 150BS bright oil, a cooling agent, an antioxidant, a brightener, a rust inhibitor and an anti-foaming agent. In the environment-friendly high-temperature isothermal graded quenching oil, The weight percentage of the 150BS bright oil is 91%, the weight percentage of the cooling agent is 5%, the weight percentage of the antioxidant is 2%, and the weight percentage of the brightener is 0.99% , the weight percentage of the anti-rust agent is 1%, and the weight percentage of the anti-foaming agent is 0.01%.

Further, the 150BS bright stock is "HVI base oil" in the enterprise standard Q/SY 44-2009 "General Lubricant Base Oil" of China National Petroleum Corporation.

Further, the cooling agent is maleic acid-ethylene-propylene terpolymer.

Further, the antioxidant is 2,6-di-tert-butyl-p-cresol.

Further, the brightening agent is imidazoline oleate.

Further, the rust inhibitor is dodecenylsuccinic acid.

Further, the antifoaming agent is dimethyl silicone oil with a viscosity of 100 cst at 25°C.

The present invention also provides a method for preparing the environment-friendly high-temperature isothermal graded quenching oil: firstly weigh 150BS bright oil, a cooling agent, an antioxidant, a brightening agent, a rust inhibitor and an anti-foaming agent according to the mass percentage, and then Add 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor and anti-foaming agent in sequence to the reaction vessel, and stir for 3 hours at 50 r/min at 60°C and normal pressure. After dissolving, it is filtered into a finished product tank to obtain the environment-friendly high temperature isothermal graded quenching oil.

Example 2

The invention provides an environment-friendly high-temperature isothermal graded quenching oil, which is composed of 150BS bright oil, a cooling agent, an antioxidant, a brightener, a rust inhibitor and an anti-foaming agent. In the environment-friendly high-temperature isothermal graded quenching oil, The weight percentage of the 150BS bright oil is 93%, the weight percentage of the cooling agent is 4%, the weight percentage of the antioxidant is 1%, and the weight percentage of the brightener is 0.97% , the weight percentage of the anti-rust agent is 1%, and the weight percentage of the anti-foaming agent is 0.03%.

Further, the 150BS bright stock is "HVI base oil" in the enterprise standard Q/SY 44-2009 "General Lubricant Base Oil" of China National Petroleum Corporation.

Further, the refrigerant is polyisobutylene.

Further, the antioxidant is dinonyldiphenylamine.

Further, the brightening agent is sorbitol monooleate.

Further, the rust inhibitor is barium petroleum sulfonate.

Further, the antifoaming agent is a copolymer of acrylate and ether.

The present invention also provides a method for preparing the environment-friendly high-temperature isothermal graded quenching oil: firstly weigh 150BS bright oil, a cooling agent, an antioxidant, a brightening agent, a rust inhibitor and an anti-foaming agent according to the mass percentage, and then Add 150BS bright oil, cooling agent, antioxidant, brightening agent, rust inhibitor and anti-foaming agent in sequence to the reaction vessel, stir at 70 ° C and normal pressure at a speed of 50 r/min for 5 hours, and wait until all materials are After dissolving, it is filtered into a finished product tank to obtain the environment-friendly high temperature isothermal graded quenching oil.

Example 3

The invention provides an environment-friendly high-temperature isothermal graded quenching oil, which is composed of 150BS bright oil, a cooling agent, an antioxidant, a brightener, a rust inhibitor and an anti-foaming agent. In the environment-friendly high-temperature isothermal graded quenching oil, The weight percentage of the 150BS bright oil is 89%, the weight percentage of the cooling agent is 7%, the weight percentage of the antioxidant is 1.98%, and the weight percentage of the brightener is 0.5% , the weight percentage of the anti-rust agent is 1.5%, and the weight percentage of the anti-foaming agent is 0.02%.

Further, the 150BS bright stock is "HVI base oil" in the enterprise standard Q/SY 44-2009 "General Lubricant Base Oil" of China National Petroleum Corporation.

Further, the cooling agent is polyisobutylene bissuccinimide.

Further, the antioxidant is N-phenyl-α-naphthylamine.

Further, the brightening agent is methyl terpene resin.

Further, the rust inhibitor is barium dinonylnaphthalene sulfonate.

Further, the antifoaming agent is dimethyl silicone oil with a viscosity of 100 cst at 25°C.

The present invention also provides a method for preparing the environment-friendly high-temperature isothermal graded quenching oil: firstly weigh 150BS bright oil, a cooling agent, an antioxidant, a brightening agent, a rust inhibitor and an anti-foaming agent according to the mass percentage, and then Add 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor and anti-foaming agent in sequence to the reaction vessel, stir at 55 ℃ and normal pressure at a speed of 50 r/min for 4 hours, and wait until all materials are After dissolving, it is filtered into a finished product tank to obtain the environment-friendly high temperature isothermal graded quenching oil.

Example 4

The invention provides an environment-friendly high-temperature isothermal graded quenching oil, which is composed of 150BS bright oil, a cooling agent, an antioxidant, a brightener, a rust inhibitor and an anti-foaming agent. In the environment-friendly high-temperature isothermal graded quenching oil, The weight percentage of the 150BS bright oil is 90%, the weight percentage of the cooling agent is 5%, the weight percentage of the antioxidant is 2%, and the weight percentage of the brightener is 1% , the weight percentage of the anti-rust agent is 1.99%, and the weight percentage of the anti-foaming agent is 0.01%.

Further, the 150BS bright stock is "HVI base oil" in the enterprise standard Q/SY 44-2009 "General Lubricant Base Oil" of China National Petroleum Corporation.

Further, the cooling agent is polyisobutylene bissuccinimide.

Further, the antioxidant is thiodipropionate.

Further, the brightening agent is imidazoline oleate.

Further, the rust inhibitor is dodecenylsuccinic acid.

Further, the antifoaming agent is a copolymer of acrylate and ether.

The present invention also provides a method for preparing the environment-friendly high-temperature isothermal graded quenching oil: firstly weigh 150BS bright oil, a cooling agent, an antioxidant, a brightening agent, a rust inhibitor and an anti-foaming agent according to the mass percentage, and then Add 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor and anti-foaming agent in sequence to the reaction vessel, and stir at 50 ℃ and normal pressure for 4 hours at a speed of 50 r/min. After dissolving, it is filtered into a finished product tank to obtain the environment-friendly high temperature isothermal graded quenching oil.

Comparative Example 1 (Chinese Patent CN 1078489A):

Composition and ratio (parts by mass): 100 parts of 650SN neutral oil, 0.5 part of sodium petroleum sulfonate, 0.1 part of random polypropylene, 0.04 part of dodecenyl succinic acid, 0.5 part of sorbitol monooleate , 0.6 part of 2,6-di-tert-butyl-p-cresol, 0.4 part of 4,4 methylene-2,6-di-tert-butylphenol.

Preparation method: the random polypropylene is mixed with the base oil at a temperature of 100-120°C, and then the mother liquor and other additives are stirred uniformly at a temperature of 70°C.

The various index data of the embodiment of the present invention and the comparative example and the petrochemical industry standard SH/T 0564-93 "Heat Treatment Oil" No. 2 isothermal graded quenching oil are listed in Table 1.

Table 1

Comparing the data of Examples 1-4 and Comparative Example 1 in Table 1, it can be seen that the flash point of the present invention is much higher, indicating that the quenching oil provided by the present invention is not easy to be lost by evaporation, and is environmentally safe; the characteristic temperature is much higher, 800->400 ℃ The cooling time of the quenching oil provided by the present invention is shortened, indicating that the cooling speed of the quenching oil provided by the present invention is greatly improved; the viscosity ratio and the increase value of the residual carbon are much lower, indicating that the thermal oxidation stability of the quenching oil provided by the present invention is significantly improved.

It can be seen from FIG. 3 that the cooling curve in the low temperature region of the embodiment 1-4 of the present invention is gentler than that of the comparative example 1, indicating that the cooling speed of the quenching oil provided by the present invention is small, and the deformation and cracking of the workpiece are minimized; The final equilibrium stabilization temperature, that is, the use temperature of the quenching oil provided by the present invention is also higher than that of Comparative Example 1, which is more conducive to obtaining a suitable bainite/martensite ratio.

The above descriptions are only a few embodiments of the present invention, and do not represent any form of limitation on the technical solutions of the present invention. Any simple modifications, equivalent changes and modifications made to the embodiments of the present invention according to the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. an environmental protection high temperature isothermal graded quenching oil, is characterized in that: be made up of 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor, antifoaming agent, in described environmental protection high temperature isothermal graded quenching oil Among them, the weight percentage of the 150BS bright oil is 89-93%, the weight percentage of the cooling agent is 3-8%, the weight percentage of the antioxidant is 1-2%, and the The weight percentage of the brightener is 0.3-1%, the weight percentage of the rust inhibitor is 1-2%, and the weight percentage of the anti-foaming agent is 0.01-0.03%. 2. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described 150BS bright stock is "HVI" in China National Petroleum Corporation Enterprise Standard Q/SY 44-2009 "General Lubricant Base Oil" base oil". 3. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described cryogen is maleic acid-ethylene-propylene terpolymer, polyisobutylene or polyisobutylene bis-succinimide Any one or a combination of two or more. 4. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described antioxidant is 2,6-di-tert-butyl-p-cresol, dinonyl diphenylamine, N-phenyl- Any one or a combination of two or more of α-naphthylamine or thiodipropionate. 5. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described brightener is any one in imidazoline oleate, sorbitol monooleate or methyl terpene resin or a combination of two or more. 6. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described rust inhibitor is any in dodecenyl succinic acid, barium petroleum sulfonate or barium dinonylnaphthalene sulfonate One or a combination of two or more. 7. environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: described antifoaming agent is the dimethyl silicone oil of 25 ℃ of viscosity 100cst or any one in acrylate and ether copolymer or combination of the two. 8. a preparation method of environmental protection high temperature isothermal graded quenching oil according to claim 1, is characterized in that: first take by weighing 150BS bright oil, cooling agent, antioxidant, brightener, rust inhibitor, anti-oxidant according to mass percentage Foaming agent, then add 150BS bright oil, cooling agent, antioxidant, brightening agent, rust inhibitor and anti-foaming agent to the reaction vessel in turn, and stir at 50 r/min at 50-70 ℃ and normal pressure. After 2 to 5 hours, after all the materials are dissolved, filter into the finished product tank to obtain the environmentally friendly high temperature isothermal graded quenching oil.

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