A solid quenching oil modifier, its preparation method and application

Abstract

This invention discloses a solid quenching oil modifier, its preparation method, and its application. The solid quenching oil modifier, by weight, comprises the following components: 70-95 parts of a cooling performance improver; 3-30 parts of an antioxidant; wherein the low-temperature antioxidant is selected from at least one of T501, BHT, T511, and di-tert-butylphenol mixtures; and the high-temperature antioxidant is selected from at least one of solid T531 and solid T534. The antioxidant includes both high-temperature and low-temperature antioxidants. Compared to liquid quenching oil modifiers, the solid quenching oil modifier of this invention has the advantages of being easier to transport, weigh, and add. Adding the solid quenching oil modifier of this invention to aged quenching oil can improve the performance of the oil in use, and improve the cooling performance and thermal oxidation stability of the aged quenching oil.

Description

Technical Field

[0001] This invention relates to a solid quenching oil modifier, its preparation method, and its application, belonging to the field of quenching reagent technology. Background Technology

[0002] Quenching is a heat treatment process in which steel is heated to a temperature above Ac3 or Ac1, held for a certain time, and then cooled at an appropriate rate to obtain a martensitic and / or bainitic structure. It is an important step in mechanical manufacturing. The purpose of quenching is to improve hardness, strength, and wear resistance to enhance the performance of parts. During quenching, quenching oil plays a crucial role as the cooling medium. Chinese invention patent application CN1078489A discloses an isothermal graded quenching oil composition, the main components of which include mineral base oil, a cooling agent, a rust inhibitor, a brightener, and an antioxidant. Chinese patent application CN103710083A discloses an isothermal graded quenching oil composition that further improves the cooling performance, thermal oxidation stability, and brightness of isothermal graded quenching oil, while also providing some short-term rust prevention.

[0003] Quenching oils naturally age over time, exhibiting characteristics such as decreased cooling performance and reduced thermal oxidation stability. These problems sometimes occur simultaneously, sometimes individually, typically leading to a decline in the quality of quenched workpieces and even the production of defective products. The usual solution is to replace some or all of the oil in use, but this incurs significant costs. Furthermore, changes in the performance of the oil during replacement can alter operating conditions, forcing heat treatment companies to invest time and effort in figuring out and adjusting equipment parameters. Adjusting the in-use oil itself can also address the issue of oil aging.

[0004] Chinese invention patent application publication CN102978356A discloses a method for regenerating quenching oil, comprising the following steps: a) settling or filtering the quenching oil to be treated; b) adding an acid value reducing agent to the quenching oil treated in step a), and contacting it fully for 0.5 to 10 hours at 65–95°C; wherein the acid value reducing agent is selected from at least one of oxides, hydroxides, or carbonates of alkali metals or alkaline earth metals, and the amount added is 0.5–3.0% of the weight of the quenching oil to be treated; c) adding an adsorption aid to the quenching oil treated in step b), and contacting it fully for 0.5–95°C. After sufficient contact for 0.5 to 10 hours, the oil is filtered; wherein the adsorption aid is selected from at least one of activated clay or diatomaceous earth, and the amount added is 5 to 15% of the weight of the quenching oil to be treated; d) the quenching oil treated in step c) is circulated and stirred at 80 to 100°C for 0.5 to 10 hours to remove trace amounts of moisture from the quenching oil, and the moisture content is controlled to be no more than 0.03% by weight; e) the functional modifier is added to the quenching oil treated in step d), and after stirring evenly, the regenerated quenching oil is obtained; wherein the amount of the functional modifier added is 0.5 to 15% of the weight of the quenching oil to be treated.

[0005] Existing methods for adding quenching oil or quenching oil functional modifiers primarily involve adding liquid substances. Liquid substances are less convenient to transport, weigh, and add than solid substances. Chinese invention patent application publication CN102978356A discloses a quenching oil regeneration method that mainly involves adding solid substances, but the process is cumbersome and requires filtration and recovery of the quenching oil after treatment. The filtered treatment agent becomes industrial waste, increasing waste disposal costs. Therefore, developing a solid quenching oil functional modifier composition that can adjust aged quenching oil without filtration and recovery has significant practical and economic implications. Summary of the Invention

[0006] To address the problem of performance degradation caused by aging of existing quenching oils during use, and the lack of a method for adjusting quenching oil using a solid modifier that does not require filtration and recovery, this invention provides a solid quenching oil modifier, its preparation method, and its application. Adding this solid quenching oil modifier to aged quenching oil improves the performance of the oil in use, significantly enhancing its cooling performance and thermal oxidation stability. In addition to adjusting aged in-use oil, this quenching oil modifier can also be used to adjust quenching oil products that are incompatible with operating conditions.

[0007] The first aspect of the present invention provides a solid quenching oil modifier, comprising, by weight, the following components: 70-95 parts of a cooling performance improver; 5-30 parts of an antioxidant; wherein the antioxidant includes a high-temperature antioxidant and a low-temperature antioxidant; the low-temperature antioxidant is selected from at least one of T501, BHT, T511, and di-tert-butylphenol; and the high-temperature antioxidant is selected from at least one of solid T531 and solid T534.

[0008] According to some embodiments of the solid quenching oil modifier of the present invention, preferably, the weight ratio of the high-temperature antioxidant to the low-temperature antioxidant is 1:0.1 to 10:1, more preferably 1:0.15 to 5:1.

[0009] According to some embodiments of the solid quenching oil modifier of the present invention, preferably, the cooling performance improver is selected from at least one of white resin and solid petroleum resin (usually with a high degree of polymerization).

[0010] In this invention, both the cooling performance improver and the antioxidant can be obtained commercially.

[0011] The second aspect of the present invention provides a method for preparing the above-mentioned solid quenching oil modifier, comprising: thoroughly mixing and grinding a cooling performance improver and an antioxidant.

[0012] According to some embodiments of the preparation method of the present invention, preferably, the grinding particle size is 80-140 mesh.

[0013] According to some specific embodiments of the preparation method described in this invention, the preparation method of the solid quenching oil modifier includes:

[0014] (1) Prepare raw materials according to the following components in parts by weight: 70-95 parts of cooling performance improver; 5-30 parts of antioxidant.

[0015] (2) Add cooling performance improver and antioxidant to the grinder and grind to 80-140 mesh to obtain better oil solubility;

[0016] (3) Take out the fully ground and mixed solid powder mixture, which is the solid quenching oil modifier.

[0017] The third aspect of the present invention provides the application of the above-mentioned solid quenching oil modifier or the above-mentioned preparation method in adjusting the properties of aged quenching oil.

[0018] The aging process refers to a decline in the cooling performance and thermal oxidation stability of the quenching oil. These problems can occur simultaneously or individually. They typically lead to a decrease in the quality of quenched workpieces, and may even result in defective products.

[0019] A fourth aspect of the present invention provides a method for adjusting the properties of aged quenching oil, comprising: adding the above-mentioned solid quenching oil modifier to the aged quenching oil, preferably, the amount added is 2% to 20% by mass.

[0020] Aged ultra-fast quenching oil usually refers to used ultra-fast quenching oil, with a maximum cooling rate (40℃) generally below 90℃ / s.

[0021] Adding solid quenching oil functional modifiers at a ratio of 2wt% to 20wt% to aged quenching oils with degraded performance can significantly improve various properties of the aged quenching oils. Regarding cooling performance, adding 5% by mass to aged high-speed quenching oil can increase the maximum cooling rate of the quenching oil from 80℃ / s to over 95℃ / s, significantly improving the cooling performance of the high-speed quenching oil. Regarding thermal oxidation stability, adding 5% by mass to aged quenching oil can increase the 150℃ rotating oxygen bomb test result from 50 min to over 105 min, significantly improving the thermal oxidation stability of the quenching oil. The addition of solid quenching oil functional modifiers significantly improves both the cooling performance and thermal oxidation stability of quenching oils, facilitating the improvement of in-use oils at a lower cost.

[0022] The beneficial effects of this invention are:

[0023] (1) The solid quenching oil modifier of the present invention can significantly improve the cooling performance and thermal oxidation stability of quenching oil, which is beneficial to improving the hardenability and hardening properties of the workpiece during the quenching process and increasing the service life of the quenching oil.

[0024] (2) The solid modifier for quenching oil of the present invention can effectively improve the overall performance of aged quenching oil. The solid modifier is easy to transport, weigh, and add, and the amount added is small. The addition method is simple, and there is no need to filter or recover the solid substances from the quenching oil after adding it. Compared with adjusting the oil in use with new oil or liquid quenching oil modifier, or adjusting the quenching oil with solid modifier that needs to be filtered and recovered, the present invention requires less time and cost, and does not generate industrial waste in the process. Detailed Implementation

[0025] To make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and are not limited to the scope of application of the present invention.

[0026] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0027] To make the technical problems, technical solutions, and beneficial effects of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely for illustrating this patent and do not limit the scope of protection of this invention in any way. Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the reagents used in the following embodiments are conventional biochemical reagents; the raw materials, instruments, and equipment used in the following embodiments can all be obtained through commercial purchase or by existing methods; the reagent dosages, unless otherwise specified, are the dosages used in conventional experimental operations; and the experimental methods, unless otherwise specified, are conventional methods.

[0028] The source of raw materials in the embodiments of the present invention:

[0029] White resin, purchased from Qisheng Trading Company, brand name 525;

[0030] Solid petroleum resin, purchased commercially from Ruisheng Chemical Co., Ltd., grade C5;

[0031] T501 was purchased from Lianlong New Materials Co., Ltd.

[0032] BHT was purchased from Jiangsu Maida New Materials Co., Ltd.

[0033] T511 was purchased from Zhejiang Jinhai Chemical Co., Ltd.

[0034] Di-tert-butyl-mixed phenols, purchased commercially from Beijing Chemical Plant No. 3;

[0035] Solid-state T531, purchased commercially from Nanjing Chemical Plant;

[0036] Solid T534, purchased commercially from PetroChina Kunlun Additives.

[0037] Example 1

[0038] Solid quenching oil modifier consists of the following components:

[0039] Cooling performance improver: white resin, 40 parts; solid petroleum resin, 40 parts;

[0040] Antioxidants: T501, 10 parts; T531, 10 parts.

[0041] Preparation method of solid quenching oil modifier: Prepare raw materials according to the above component weight parts, add cooling performance improver and antioxidant to grind in a grinder to 80-140 mesh to obtain better oil solubility, take out the fully ground and mixed solid powder mixture to obtain solid quenching oil modifier 1#.

[0042] Example 2

[0043] Solid quenching oil modifier consists of the following components:

[0044] Cooling performance improver: 20 parts white resin; 65 parts solid petroleum resin.

[0045] Antioxidant: BHT, 10 parts; solid T534, 5 parts.

[0046] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 2#.

[0047] Example 3

[0048] Solid quenching oil modifier consists of the following components:

[0049] Cooling performance improver: white resin, 70 parts.

[0050] Antioxidants: 20 parts of di-tert-butyl phenol mixture; 10 parts of solid T534.

[0051] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 3#.

[0052] Example 4

[0053] Solid quenching oil modifier consists of the following components:

[0054] Cooling performance improver: solid petroleum resin, 95 parts.

[0055] Antioxidants: 3 parts di-tert-butylphenol mixture; 2 parts solid T531.

[0056] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 4#.

[0057] Example 5

[0058] Solid quenching oil modifier consists of the following components:

[0059] Cooling performance improver: 50 parts white resin; 25 parts solid petroleum resin.

[0060] Antioxidant: BHT, 20 parts; solid T534, 5 parts.

[0061] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 5#.

[0062] Example 6

[0063] Solid quenching oil modifier consists of the following components:

[0064] Cooling performance improver: white resin, 40 parts; solid petroleum resin, 40 parts.

[0065] Antioxidants: T501, 10 parts; T511, 5 parts; solid T531, 5 parts.

[0066] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 6#.

[0067] Example 7

[0068] Solid quenching oil modifier consists of the following components:

[0069] Cooling performance improver: 30 parts white resin; 40 parts petroleum resin.

[0070] Antioxidants: BHT, 10 parts; solid T531, 10 parts; solid T534, 10 parts.

[0071] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier 7#.

[0072] Comparative Example 1

[0073] Solid quenching oil modifier consists of the following components:

[0074] Antioxidants: T501, 20 parts; T511, 20 parts; di-tert-butyl phenol mixture, 20 parts; solid T531, 20 parts; solid T534, 20 parts.

[0075] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier A.

[0076] Comparative Example 2

[0077] Solid quenching oil modifier consists of the following components:

[0078] Cooling performance improver: 50 parts white resin; 50 parts solid petroleum resin.

[0079] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier B.

[0080] Comparative Example 3

[0081] Solid quenching oil modifier consists of the following components:

[0082] Cooling performance improver: white resin, 40 parts; solid petroleum resin, 30 parts.

[0083] Antioxidants: T501, 10 parts; T511, 10 parts; di-tert-butyl phenol mixture, 10 parts.

[0084] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier C.

[0085] Comparative Example 4

[0086] Solid quenching oil modifier consists of the following components:

[0087] Cooling performance improver: white resin, 40 parts; solid petroleum resin, 30 parts;

[0088] Antioxidants: Solid T531, 15 parts; Solid T534, 15 parts.

[0089] Preparation method of solid quenching oil modifier: The method of Example 1 was followed to obtain solid quenching oil modifier D.

[0090] Comparative Example 5

[0091] According to Example 1 of patent document CN103710083A, quenching oil was prepared to obtain solid quenching oil modifier E.

[0092] Test case

[0093] The aged ultra-fast quenching oil used in this test refers to used U8121 ultra-fast quenching oil with a maximum cooling rate (40℃) of less than 90℃ / s.

[0094] The solid quenching oil modifiers prepared in Examples 1-7 and Comparative Examples 1-5 were added at a mass fraction of 5% to aged ultra-fast quenching oil to improve the performance of the aged quenching oil. The results are shown in Table 1.

[0095] (1) The maximum cooling rate is tested according to ISO 9950;

[0096] (2) The test method for rotating oxygen bomb shall be carried out in accordance with SH / T 0193.

[0097] Table 1

[0098]

[0099]

[0100] Comparing the maximum cooling rate (40°C) before and after adding solid quenching oil functional modifier in Examples 1-7, it can be seen that adding solid quenching oil functional modifier at a mass fraction of 5% can increase the maximum cooling rate of aged quenching oil from 80°C / s to over 95°C / s, significantly improving the cooling performance of quenching oil and helping to improve the hardenability and hardenability of the workpiece during the quenching process.

[0101] Comparing the rotating oxygen bombs (150°C) before and after adding solid quenching oil functional modifier in Examples 1-7, it can be seen that adding solid quenching oil functional modifier at a mass fraction of 5% can increase the rotating oxygen bomb of aged quenching oil from 50 min to over 105 min, significantly improving the thermal oxidation stability of quenching oil and thus helping to extend its service life.

[0102] Comparing the maximum cooling rate (40°C) before and after adding solid quenching oil functional modifier in Comparative Example 1, it can be seen that adding 5% by mass of the comparative example cannot increase the maximum cooling rate (40°C) of the aged quenching oil. This indicates that the improvement in the cooling performance of the quenching oil in Examples 1 to 7 is the effect of the cooling performance improver in the solid quenching oil functional modifier.

[0103] Comparing the rotating oxygen bomb (150°C) before and after adding solid quenching oil functional modifier in Comparative Example 2, it can be seen that adding 5% by mass of the comparative example cannot increase the rotating oxygen bomb value of the aged quenching oil. This indicates that the improvement in the thermal oxidation stability of the quenching oil in Examples 1 to 7 is the effect of the antioxidant in the solid quenching oil functional modifier.

[0104] Comparing the rotating oxygen bombs (150°C) before and after adding solid quenching oil functional modifier in Comparative Example 3, it can be seen that adding 5% by mass of the comparative example has a limited effect on improving the rotating oxygen bomb value of aged quenching oil. This indicates that the improvement in the thermal oxidation stability of quenching oil in Examples 1 to 7 is related to the high-temperature antioxidant in the solid quenching oil functional modifier.

[0105] Comparing the rotating oxygen bombs (150°C) before and after adding solid quenching oil functional modifier in Comparative Example 4, it can be seen that adding 5% by mass of the comparative example has a limited effect on improving the rotating oxygen bomb value of aged quenching oil. This indicates that the improvement in the thermal oxidation stability of quenching oil in Examples 1 to 7 is related to the low-temperature antioxidant in the solid quenching oil functional modifier.

[0106] Compared to Comparative Examples 1-5, the solid quenching oil regulator of the present invention has superior performance.

[0107] The above experimental results demonstrate that solid quenching oil functional modifiers can effectively improve the overall performance of aged quenching oil and significantly enhance its cooling performance and thermal oxidation stability.

[0108] The above description is merely a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, based on the technical teachings provided by the present invention and as common knowledge in the field, other equivalent modifications and improvements can be made, and these should also be considered within the scope of protection of the present invention.

Claims

1. A solid quenching oil conditioner, consisting of 70-95 parts by weight of a cooling performance improver and 5-30 parts of an antioxidant; the antioxidant comprises a high temperature antioxidant and a low temperature antioxidant; the low temperature antioxidant is selected from at least one of T501, BHT, T511, and di-tert-butyl mixed phenol; the high temperature antioxidant is selected from at least one of solid T531 and solid T534; the cooling performance improver is selected from solid petroleum resin, white resin of grade 525, a mixture of solid petroleum resin and white resin of grade 525. The weight ratio of the high temperature antioxidant to the low temperature antioxidant is 1:0.1-10:

1.

2. The solid-state quenching oil conditioner according to claim 1, characterized by, The weight ratio of the high temperature antioxidant to the low temperature antioxidant is 1:0.15-5:

1.

3. The solid-state quenching oil conditioner according to claim 1, characterized by, The cooling performance improver and the antioxidant are mixed and ground to obtain the solid quenching oil conditioner.

4. A method of preparing the solid-state quenching oil conditioner of any one of claims 1 to 3, comprising: The particle size after grinding is 80-140 mesh.

5. The method of producing the solid quenching oil conditioner as claimed in claim 4, characterized by, 6. Use of the solid quenching oil conditioner of any one of claims 1-3 or the solid quenching oil conditioner prepared by the preparation method of claim 4 or 5 in conditioning the performance of aged quenching oil. The solid quenching oil conditioner of any one of claims 1-3 or the solid quenching oil conditioner prepared by the preparation method of claim 4 or 5 is added to aged quenching oil.

7. A method of adjusting the performance of an aged quenching oil comprising: The addition amount of the solid quenching oil conditioner is 2%-20% of the mass of the aged quenching oil.

8. The method of adjusting the performance of an aged quench oil according to claim 7, characterized in that, ​

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