CN110747320B - Low-temperature coolant for overspeed quenching oil - Google Patents
Low-temperature coolant for overspeed quenching oil Download PDFInfo
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- CN110747320B CN110747320B CN201910992972.6A CN201910992972A CN110747320B CN 110747320 B CN110747320 B CN 110747320B CN 201910992972 A CN201910992972 A CN 201910992972A CN 110747320 B CN110747320 B CN 110747320B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
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Abstract
The invention discloses an overspeed quenching oil low-temperature coolant, which is prepared by compounding synthetic sodium sulfonate A and synthetic sodium sulfonate B, wherein the weight ratio of A: b is 1-4: 1; the synthetic sodium sulfonate A is sodium Heavy Alkyl Benzene Sulfonate (HABS), and the synthetic sodium sulfonate B is selected from synthetic sodium sulfonate B (r) or synthetic sodium sulfonate B (r). The low-temperature cooling catalyst combination adopted has excellent heat resistance, ageing resistance and emulsifying and dispersing performance, reduces the convection starting temperature in the cooling process, and ensures that the low-temperature cooling speed is higher and better maintained.
Description
Technical Field
The invention relates to the technical field of metal material heat treatment, in particular to a cooling catalyst for quenching oil.
Background
The modern machine manufacturing industry puts higher requirements on the heat treatment technology, and aims to solve the problems of low quenching hardness and shallow quenching through layer of large parts and forged parts of metal materials. The quenching of the large-scale zero forging piece needs the ultra-speed quenching oil with higher cooling speed and higher stability, including the excellent cooling speed of a high-temperature area and the continuous and effective cooling speed of a low-temperature area, so that the transformation quantity of martensite can be ensured, and the hardenability are improved. See: the book of quenching oil (general description of quenching oil) — Heat treatment techniques and Equipment (vol. 28, 2 nd phase, 4 months in 2007, Yanggui Sheng, etc.; high-speed cooling quenching oil for metals (U.S. Pat. No. 3981150) — foreign Metal Heat treatment, 6 th 1989, Lewanhai; relationship between quenching medium cooling characteristic curve and quenching effect of steel (Wuhan university of automobile university, 1997, 4 th Ed., Hu Shi Dong, et al).
In the prior art, the cooling capacity of the commercial overspeed quenching oil is deteriorated too fast along with the service cycle, and the added low-temperature catalyst is poor in heat resistance and is decomposed almost completely after a while, so that the low-temperature acceleration effect is lost, the quenching process enters a low-temperature convection stage too early, and the quenching cooling capacity is influenced.
Disclosure of Invention
In order to solve the disadvantages, the invention aims to provide a novel low-temperature coolant for overspeed quenching oil, which has strong cooling capacity, high temperature resistance and excellent continuous effective performance. In order to solve the technical problems, the invention adopts the technical scheme that the low-temperature cooling catalyst for the overspeed quenching oil is characterized by being prepared by compounding synthetic sodium sulfonate A and synthetic sodium sulfonate B according to the weight ratio of A: b is 1-4: 1; the preferable mixture ratio is A, B is 1: 1; a, B is 1.5: 1; a, B is 2: 1;
the synthetic sodium sulfonate A adopts sodium heavy alkylbenzene sulfonate (HABS) and is prepared from various long-chain alkylbenzenesThe mixture is brown yellow viscous liquid or semisolid, the sulfonate content is 72 wt%, the average molecular weight is 560, the flash point is 215 ℃, the ignition point is 230 ℃, and the kinematic viscosity at 100 ℃ is 245mm2And s. Such as sodium Heavy Alkyl Benzene Sulfonate (HABS) T702A from Nanjing Hengxiong chemical Co.
The synthetic sodium sulfonate B is selected from the following (I) or (II):
the synthetic sodium sulfonate B (I) is prepared from a mixture of a plurality of branched alkylbenzene, is a black viscous liquid or semisolid, has the sulfonate content of 50 percent by weight, the average molecular weight of 425, the flash point of 150 ℃ and the kinematic viscosity of 95mm at 100 DEG C2S; such as sodium sulfonate synthesized by TecGARD 260A available from Chemical Limited of Afton (Afton Chemical Corporation).
The synthetic sodium sulfonate B is prepared from a mixture of a plurality of branched alkylbenzene, is brown yellow viscous liquid or semisolid, has the sulfonate content of 74 percent by weight, the average molecular weight of 520, the flash point of 210 ℃, and the kinematic viscosity of 410mm at 100 DEG C2/s。
And uniformly mixing the synthetic sodium sulfonate A and the synthetic sodium sulfonate B.
The invention has the beneficial effects that the adopted low-temperature cooling catalyst combination has excellent heat resistance, ageing resistance and emulsifying and dispersing performance, the convection starting temperature in the cooling process is reduced, the low-temperature cooling speed is higher and better maintained (the cooling speed of quenching oil at 300 ℃ is about 6-30 ℃/s).
The low-temperature coolant is applied to overspeed quenching oil. Preferably, the overspeed quenching oil consists of the following components in percentage by weight: 88-95 wt% of base oil, 0.5-1 wt% of high-temperature antioxidant, 1-3 wt% of antirust agent, 2-5 wt% of high-temperature refrigerant and 1-4 wt% of low-temperature refrigerant; wherein:
the base oil is selected from one or a mixture of more than one of three types of hydrogenated oil with low viscosity (about 10) in any proportion; preferably, the viscosity index of the base oil is more than or equal to 100, the flash point is more than or equal to 180 ℃, and the kinematic viscosity at 40 ℃ is 9-12 mm2/s。
The high-temperature antioxidant can be selected from commercial high-temperature antioxidants such as T501(2, 6-di-tert-butyl-p-cresol), T532 (containing benzotriazole derivative complexing agent) and the like. Preferably, the high-temperature antioxidant is a high-temperature-resistant organic amine antioxidant and an organic phenol antioxidant which are matched for use; the weight ratio is that, the organic amine antioxidant: 1-3 parts of organic phenol antioxidant: 1. further preferably, the flash point of the organic amine antioxidant is more than or equal to 250 ℃, and the flash point of the organic phenol antioxidant is more than or equal to 180 ℃.
The rust inhibitor may be selected from commercially available rust inhibitor products. Preferably, the antirust agent is selected from one of barium petroleum sulfonate (chemical common name: T701) or barium dinonyl naphthalene sulfonate (chemical common name: T705). Such as T701 or T705 from Nanjing Shengxiong chemical company Limited.
The high temperature catalyst may be selected from commercially available products. Such as oil soluble high molecular polymer, ethylene propylene diene monomer copolymer, polyisobutylene, petroleum resin KENDEX 0834, etc.
Preferably, the high-temperature catalyst is prepared by compounding polyisobutylene PIB2400 and PIB1300 with two different molecular weights, and the weight ratio of the polyisobutylene PIB2400 to the polyisobutylene PIB1300 is as follows: PIB1300 ═ 1.5:1, where the kinematic viscosity at 100 ℃ of PIB2400 was 4800mm2(s) a kinematic viscosity at 100 ℃ of 600mm for PIB13002And s. Such as PIB2400 and PIB1300, available from ten thousand trade ltd, guangzhou.
The preparation method of the overspeed quenching oil sequentially comprises the following steps:
adding base oil and a high-temperature refrigerant into a reaction kettle according to a proportion, and heating until the high-temperature refrigerant is dissolved;
and step two, adding the low-temperature cooling catalyst, the high-temperature antioxidant and the antirust agent into the reaction kettle in proportion, and stirring for not less than 30 minutes to obtain the overspeed quenching oil.
The overspeed quenching oil adopts a compound additive formula, can simultaneously ensure higher cooling speed of a high-temperature area and continuous effective cooling speed of a low-temperature area of the overspeed quenching oil, can adapt to severe quenching working environment, has the anti-attenuation capability of the cooling speed superior to that of the similar products sold in the market, and continuously and effectively works so as to ensure excellent quenching performance of workpieces, and specifically comprises the following aspects:
1. the quenching cooling speed is ultra-fast, and the quenching cooling device is suitable for quenching large-scale workpieces and materials with poor hardenability, such as large-scale bearing steel, tool and die steel, heat-resistant steel and other workpieces, and can also be used for carbon steel workpieces with the diameter of about 16mm, and can partially replace aqueous quenching medium for quenching, and achieve better quenching hardness and metallographic structure.
2. The high-temperature refrigerant and the low-temperature refrigerant cannot interfere with each other in functionality, and meanwhile, the A/B component of the low-temperature refrigerant takes effect synergistically, so that the low-temperature cooling speed is greatly improved, and the stability is good.
3. The overspeed quenching oil has high flash point, good safety and stable integral cooling performance, and can adapt to the working environment of long-term high-temperature and continuous operation.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Drawings
FIG. 1 is a cooling curve diagram of 60 ℃ conventional test detection of novel overspeed quenching oil;
FIG. 2 is a comparison graph of the front and back of a test and detection report of the novel overspeed quenching oil which is heated to 130 ℃ for several times and is kept warm for 30 minutes;
FIG. 3 is a graph comparing curves before and after heating up to 130 deg.C and maintaining for 30 min.
Detailed Description
Preparation example 1: the components and the mass ratio thereof in the embodiment are as follows:
93.0 percent of base oil, adopts paraffin-based white oil, and has the viscosity index of more than or equal to 100, the flash point of more than or equal to 180 ℃, and the kinematic viscosity of 9-12 mm at 40 DEG C2/s。
0.5% of high-temperature antioxidant, and a high-temperature resistant organic amine antioxidant and an organic phenol antioxidant are used in a matching way, wherein the organic amine antioxidant adopts Pasteur Ciba IRGANOX L57, the organic phenol antioxidant adopts Pasteur Ciba IRGANOX L135, the Pasteur Ciba IRGANOX L57 and the Pasteur Ciba IRGANOX XL135 are compounded according to the weight ratio of L57: L135-1.5: 1.
1% of antirust agent, adopting barium petroleum sulfonate, and T701 produced by Nanjing Shengxiong chemical industry Co.
4% of high-temperature refrigerant, and petroleum resin KENDEX 0834 (low-viscosity black viscous petroleum resin in the producing America) is adopted.
1.5 percent of low-temperature refrigerant, and is formed by compounding synthetic sodium sulfonate A and synthetic sodium sulfonate B, wherein the compounding weight ratio is synthetic sodium sulfonate A: synthetic sodium sulfonate B ═ 2: 1.
the synthetic sodium sulfonate A is prepared from multiple long-chain alkylbenzene mixtures, such as sodium dialkylbenzenesulfonate T702A (HABS) from Nanjing stamen chemical Limited, and is brown yellow viscous liquid or semisolid, with sulfonate content of 72 wt%, average molecular weight of 560, flash point of 215 deg.C, ignition point of 230 deg.C, and kinematic viscosity of 245mm at 100 deg.C2/s。
Synthetic sodium sulfonate B II is synthetic sodium sulfonate (T702B) produced by Nanjing Shengxiong chemical Co. Is prepared from the mixture of several branched alkylbenzenes, and is a brown yellow viscous liquid or semisolid, with sulfonate content of 74 wt%, average molecular weight of 520, flash point of 210 deg.C, kinematic viscosity of 410mm at 100 deg.C2/s。
The synthetic sodium sulfonate A and the synthetic sodium sulfonate B are mixed evenly.
The preparation method sequentially comprises the following steps:
firstly, in a blending reaction kettle, heating the base oil to 60 ℃, and simultaneously heating a high-temperature refrigerant to 60 ℃ for dissolving;
and secondly, adding the low-temperature cooling catalyst, the antioxidant and the antirust agent into a blending reaction kettle, and then fully stirring for 30 minutes to obtain the overspeed quenching oil. The novel overspeed quenching oil prepared in the embodiment is randomly sampled and subjected to the following detection, and the physical and chemical indexes of the novel overspeed quenching oil are shown in a table (1):
TABLE 1 physicochemical indexes of novel overspeed quenching oil
The cooling curve chart of the 60 ℃ conventional test data of the novel ultra-speed quenching oil prepared in the embodiment is shown in figure 1: FIG. 1 illustrates: a method for evaluating hardenability of a quenching oil is used. Numerical evaluation method: (segerberg method) HP 91.5+1.347Tvp +10.88CR-3.85 Tcp. In the formula: hp is the quenching capacity of quenching oil; tvp-characteristic temperature; CR, average cooling speed at 500-600 ℃, DEG C/s; TCP-start temperature of convection phase, c; HP value above 1200 is an ultrastrong value.
The novel overspeed quenching oil prepared by the embodiment is tested by repeatedly heating up to 130 ℃ and preserving heat for 30 minutes, and the front and back comparison curve graphs are shown in figure 2:
in FIG. 2, the cooling curve 010005 shows a higher HP value in the HP-91.5 + 1.347X 720+ 10.88X 105-3.85X 250HP ≧ 1200 cooling curves 010002, 01003, 010004. Indicating excellent hardenability.
For the purpose of providing a comparative illustration, the overspeed quench oil comparative sample H was also tested by multiple temperature increases to 130 ℃ for 30 minutes, and the graphs before and after comparison are shown in fig. 3. The overspeed quenching oil comparison sample H consists of the following components in parts by weight: 94% of 10# white oil, 4% of high-temperature refrigerant 0834, 0.5% of antioxidant L57: l135 ═ 1.5:1, 1% of an antirust agent T701; 0.5% of low-temperature catalyst T702. The difference between the overspeed quenching oil comparison sample H and the novel overspeed quenching oil sample of the invention is as follows: the low-temperature catalyst of the overspeed quenching oil comparative sample H adopts a common catalyst T702 purchased by Wanhe trading Co., Ltd, Guangzhou.
As can be seen from FIG. 3, the maximum cooling rate of the conventional test data of the ordinary ultra-speed quenching oil is 113 ℃/S, the cooling rate of 300 ℃ is 24 ℃/S, and the quenching cooling capacity is stronger. However, the test result is greatly changed after 30 minutes of one 130-degree heat preservation, particularly the cooling speed of 300 degrees is as low as 6 ℃/S, which is the lowest low-temperature cooling speed of the base oil, and the reheating heat preservation test loses significance.
Preparation example 2: the difference from preparation example 1 lies in the adjustment of the components and the mass ratio thereof, see table (2) below, the preparation methods are all the same as preparation example 1, the physicochemical indexes and the performance test data such as cooling curves support the conclusion of example 1, and the details are not repeated:
TABLE (2) Components and their mass ratios in preparative example 2
Preparation example 3: the difference from preparation example 1 lies in the adjustment of the components and the mass ratio thereof, see table (3) below, the preparation methods are all the same as preparation example 1, the physicochemical indexes and the performance test data such as cooling curves support the conclusion of example 1, and the details are not repeated:
TABLE (3) preparation of the components of example 3 and their mass ratios
Claims (9)
1. The low-temperature cooling catalyst for the overspeed quenching oil is characterized by being prepared by compounding synthetic sodium sulfonate A and synthetic sodium sulfonate B in a weight ratio of the synthetic sodium sulfonate A: and (3) synthetic sodium sulfonate B is 1-4: 1;
the synthetic sodium sulfonate A is prepared from sodium heavy alkylbenzene sulfonate, is a brown yellow viscous liquid or semisolid prepared from a mixture of a plurality of long-chain alkylbenzenes, has the sulfonate content of 72 wt%, the average molecular weight of 560, the flash point of 215 ℃, the ignition point of 230 ℃ and the kinematic viscosity of 245mm at 100 DEG C2/s；
The synthetic sodium sulfonate B is selected from the following (I) or (II):
synthesizing sodium sulfonate BA mixture of branched alkylbenzenes in the form of a black viscous liquid or semisolid having a sulfonate content of 50% by weight, an average molecular weight of 425, a flash point of 150 ℃ and a kinematic viscosity of 95mm at 100 DEG C2/s；
The synthetic sodium sulfonate B is prepared from a mixture of a plurality of branched alkylbenzene, is brown yellow viscous liquid or semisolid, has the sulfonate content of 74 percent by weight, the average molecular weight of 520, the flash point of 210 ℃, and the kinematic viscosity of 410mm at 100 DEG C2/s。
2. The low-temperature refrigerant catalyst according to claim 1, wherein the weight ratio of the synthetic sodium sulfonate A to the synthetic sodium sulfonate B is as follows, the synthetic sodium sulfonate A to the synthetic sodium sulfonate B is 1: 1.
3. the low-temperature refrigerant catalyst according to claim 1, wherein the weight ratio of the synthetic sodium sulfonate A to the synthetic sodium sulfonate B is 1.5: 1.
4. the low-temperature refrigerant catalyst according to claim 1, wherein the weight ratio of the synthetic sodium sulfonate A to the synthetic sodium sulfonate B is as follows, the synthetic sodium sulfonate A to the synthetic sodium sulfonate B is 2: 1.
5. the use of the low-temperature catalyst in the overspeed quenching oil according to any one of claims 1 to 4, wherein the overspeed quenching oil using the low-temperature catalyst comprises the following components in parts by weight: 88-95 wt% of base oil, 0.5-1 wt% of high-temperature antioxidant, 1-3 wt% of antirust agent, 2-5 wt% of high-temperature refrigerant and 1-4 wt% of low-temperature refrigerant.
6. The use according to claim 5, wherein the base oil is selected from one or more of paraffin-based white oil, paraffin-based transformer oil, and low-viscosity hydrogenated oils in any proportion; the viscosity index of the base oil is more than or equal to 100, the flash point is more than or equal to 180 ℃, and the kinematic viscosity at 40 ℃ is 9-12 mm2/s。
7. The use of claim 5, wherein the high-temperature antioxidant is a mixture of high-temperature-resistant organic amine antioxidant and organic phenol antioxidant; the weight ratio is that, the organic amine antioxidant: 1-3 parts of organic phenol antioxidant: 1; the flash point of the organic amine antioxidant is more than or equal to 250 ℃, and the flash point of the organic phenol antioxidant is more than or equal to 180 ℃.
8. The use of claim 5 wherein the rust inhibitor is selected from one of barium petroleum sulfonate or barium dinonylnaphthalene sulfonate.
9. The application of claim 5, wherein the high-temperature catalyst is prepared by compounding polyisobutylene PIB2400 and PIB1300 with two different molecular weights, and the weight ratio of the polyisobutylene PIB2400 to the polyisobutylene PIB1300 is as follows: PIB1300 ═ 1.5:1, where the kinematic viscosity at 100 ℃ of PIB2400 was 4800mm2(s) a kinematic viscosity at 100 ℃ of 600mm for PIB13002/s。
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| CN111471842A (en) * | 2020-04-10 | 2020-07-31 | 南京科润工业介质股份有限公司 | Over-speed bright quenching oil with stable cooling speed |
| CN111560503A (en) * | 2020-05-27 | 2020-08-21 | 中国石油化工股份有限公司 | Isothermal graded quenching oil composition for bearing, preparation method and application thereof |
| CN113817904A (en) * | 2021-08-11 | 2021-12-21 | 富兰克润滑科技（太仓）有限公司 | Low-carbon environment-friendly biodegradable quenching oil and preparation method thereof |
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| CN104313266A (en) * | 2014-09-30 | 2015-01-28 | 宁波保润石化有限公司 | Rapid bright quenching oil and preparation method thereof |
| CN105063294A (en) * | 2015-08-11 | 2015-11-18 | 广西大学 | Environmental-friendly low-temperature tempering liquid composite |
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