CN108559600B

CN108559600B - Emulsion for fine processing of steel workpiece, preparation method and post-treatment process thereof

Info

Publication number: CN108559600B
Application number: CN201810006018.0A
Authority: CN
Inventors: 白林森; 梁莲芝
Original assignee: Shanghai Lika Environmental Protection Technology Co ltd
Current assignee: Shanghai Lika Environmental Protection Technology Co.,Ltd.
Priority date: 2018-01-03
Filing date: 2018-01-03
Publication date: 2021-04-20
Anticipated expiration: 2038-01-03
Also published as: CN108559600A

Abstract

The invention provides a formula composition of an emulsion for fine processing of steel workpieces, a preparation method and a post-treatment method thereof, wherein the emulsion comprises refined mechanical composite base oil, composite ester, an anionic surfactant, an organosilicon nonionic surfactant, an extreme pressure agent, a bactericide, a pH value regulator and non-tap water with the hardness of less than 200 ppm. The emulsion has the advantages of excellent lubricating property, good corrosion resistance, strong stability, long service life, simple method for preparing the emulsion, less components, no environmental pollution of the treated waste emulsion, and cyclic utilization of the separated oil phase.

Description

Emulsion for fine processing of steel workpiece, preparation method and post-treatment process thereof

Technical Field

The invention relates to the field of metal product processing, in particular to an emulsion for fine processing of a steel workpiece, a preparation method and a post-treatment process thereof.

Background

The emulsion is used as a lubricant for various machining processes of cutting, stamping, rolling, drawing and the like of metals and alloys thereof, and has the functions of preventing metal parts from rusting, taking away heat generated in the machining process, effectively removing cuttings and other particles on the surfaces of the parts and cutters and the like. The first emulsions touched were pure water, and then water or oil based emulsions were slowly developed.

Depending on the composition and medium of the emulsion, emulsions can be divided into two categories, oil-based and water-based: (1) the oil-based emulsion is prepared by adding an oily antirust agent and other oily additives including extreme pressure agents containing chlorine, phosphorus and sulfur into an oil-based compound (mineral oil and vegetable oil). Its advantages are high lubricating and antirust performance, poor cooling effect, and easy generation of oil mist and oil soot, and fire. (2) Water-based emulsion: the water-based emulsion has the advantages of large specific heat of water, high thermal conductivity, large heat of vaporization, excellent cooling performance, low cost and convenient cleaning after processing, and the water-based emulsion mainly comprises three types, namely emulsion, semi-synthetic liquid and synthetic liquid. The emulsion has high oil content, consists of water-insoluble mineral oil, fatty oil and a surfactant, and has good lubricity and machinability; the semisynthetic liquid consists of a small amount of mineral oil, a proper amount of water and a proper amount of additives, has wide applicability, and has longer service life, corrosion resistance and extreme pressure performance than those of the emulsion; the synthetic liquid contains a large amount of water and various water-soluble functional additives, but does not contain oil, is in a transparent state after being diluted by water, has good cooling property and poor lubricating property, and is easy to cause corrosion of workpieces. At present, the emulsion which is the mainstream is a semi-synthetic emulsion and has the excellent characteristics of the emulsion and a synthetic liquid, but the emulsion and the synthetic liquid still have the defects of the emulsion and the synthetic liquid, for example, the semi-synthetic water-based emulsion is easy to be attacked by microorganisms due to the components such as mineral oil, fatty acid soap, amine, sulfonate, water and the like, so that the putrefaction is caused, and the service life is shortened. Particularly, the use period in hot summer in the south is only one week, even two or three days, so that the odor is smelled, and a lot of troubles are brought to operators. The working time and the production cost for replacing the processing fluid are increased, the working environment is polluted, and for example, the semi-synthetic water-based emulsion contains a large amount of water, so that the lubricity, the machinability and the corrosion resistance of the emulsion are all required to be improved.

In addition, for the fine cutting steel substrate, the lubricity and machinability of synthetic liquid and semisynthetic liquid are far from reaching the manufacturing standard, and at this time, the excellent lubricity and machinability of the emulsion are important, but the service life is too short, and the lubricity and machinability are still to be improved, and the waste emulsion after use is also in urgent need of treatment.

Disclosure of Invention

In order to solve the problems of the prior emulsion mentioned in the background art, the invention provides the emulsion for the fine processing of the steel workpiece, a preparation method of the emulsion and a treatment process of emulsion waste liquid.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the emulsion for fine machining of the steel workpiece comprises the following components in percentage by mass:

refining mechanical composite base oil: the mixture of sulfonated castor oil and one of L-AN10, L-AN15 or L-AN32 in the mass ratio of 1: (0.2-0.4), total 20-65 wt.%;

compound ester: 3-15 wt.% of oleic acid isopropanolamine boric acid composite ester;

anionic surfactant: 0.5-1 wt.% of sodium petroleum sulfonate;

silicone nonionic surfactant: 0.05-0.2 wt.% of polyether modified silicone oil;

extreme pressure agent: 1-5 wt.% of zinc dialkyldithiophosphate or alkanoate ester of cyclohexanediol;

and (3) bactericide: 1-2 wt.% of one or more of methylisothiazolone, methylene dichloride phenol or methylene dimorpholine;

pH value regulator: NaOH or Na₂CO₃Adjusting the pH value to 8-10;

the remainder was non-tap water, with water hardness <200 ppm.

The invention also provides a preparation method of the emulsion, which comprises the following steps: firstly, oleic acid, boric acid and isopropanolamine are mixed according to a molar ratio of 1: (1-2): (4-6) 140-155^oPerforming esterification reaction for 2-3 h under C, cooling, and standing to obtain a composite ester A solution; then weighing a certain proportion of refined machine oil and sulfonated castor oil, placing them into a reaction kettle, adding a proper quantity of composite ester A solution, and adding 60-80% of composite ester A solution^oC, slowly stirring for 1-2 h to obtain an oil phase B liquid which is uniformly mixed; then weighing the hardness<200ppm of non-tap water is put into a stirring reaction kettle, then sodium petroleum sulfonate and polyether modified silicone oil are added into the stirring reaction kettle, and the stirring reaction kettle is heated to 60 to 80 DEG^oC, stirring for 1-2 h to obtain a uniform solution C, then pouring the solution C into the solution B, mixing, and mixing 60-80%^oC, stirring for 0.5h under heat preservation to obtain uniform O/W emulsion, and then cooling to 40 DEG^oC, adding an extreme pressure agent and a bactericide, continuously stirring for 1-1.5 h, cooling to room temperature, and then using NaOH or Na₂CO₃And adjusting the pH value of the emulsion to 8-10 to finally obtain the emulsion for fine processing of the steel workpiece.

The invention further provides a post-treatment method of the emulsion for fine processing of steel workpieces, which is characterized in that the emulsion is used waste emulsion, the used waste emulsion is firstly collected in a collection box, solid steel scrap impurities and liquid are separated through a centrifugal machine and a filter, and then 5wt.% of mixed liquid of sulfuric acid, hydrochloric acid and calcium chloride is added into the liquid, wherein the mass ratio of the sulfuric acid to the hydrochloric acid to the calcium chloride is 1: 0.5: (0.1-0.3), the pH value of the liquid is 6-7, so that the oil and the wastewater are separated, the obtained wastewater is treated by an active coal adsorption and electrocoagulator to remove redundant organic substances, the wastewater is purified, the oil content of the finally discharged wastewater is lower than 5mg/L, the suspended matters are lower than 300mg/L, the Chemical Oxygen Demand (COD) is lower than 80mg/L, and the obtained oil phase is subjected to high-temperature sterilization and impurity removal and can be recycled to be used as emulsion base oil for fine processing of steel workpieces.

Advantageous effects

The invention can achieve the following beneficial technical effects:

(1) the emulsion has simple preparation process and convenient use, and is particularly suitable for fine cutting manufacturing of steel parts;

(2) the emulsion is safe and environment-friendly, the cost is low, and the oil phase of the emulsion can be recycled;

(3) the emulsion has the advantages of excellent lubricating property, good corrosion resistance, strong stability, long service life, excellent cleaning property, rust resistance, cooling property, processing visibility and the like.

Detailed Description

Comparative example 1

A steel workpiece emulsion, the emulsion comprising:

base oil: L-AN15, 40 wt.%;

compound ester: oleic isopropanolamine boronic acid complex ester, 10 wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.75 wt.%;

silicone nonionic surfactant: 0.1 percent of polyether modified silicone oil;

extreme pressure agent: zinc dialkyldithiophosphates; 3wt.%;

and (3) bactericide: methylisothiazolone, 1wt.%;

pH value regulator: na (Na)₂CO₃Adjusting the pH value to 8-10;

the rest is non-tap water, and the hardness of the water is less than 200 ppm; labeled D-1.

Comparative example 2

A steel workpiece emulsion, the emulsion comprising:

refining mechanical composite base oil: the mixture of L-AN15 and sulfonated castor oil is prepared from the following components in a mass ratio of 1: 0.3, 40 wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.75 wt.%;

silicone nonionic surfactant: 0.1 percent of polyether modified silicone oil;

extreme pressure agent: zinc dialkyldithiophosphates; 3wt. -%)

And (3) bactericide: methylisothiazolone, 1wt.%;

pH value regulator: na (Na)₂CO₃Adjusting the pH value to 8-10;

the rest is non-tap water, and the hardness of the water is less than 200 ppm; labeled D-2.

Comparative example 3

A steel workpiece emulsion, the emulsion comprising:

oleic acid, 1.25wt. -%)

Boric acid, 2.5wt. -%)

Isopropanolamine, 6.25 wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.75 wt.%;

silicone nonionic surfactant: 0.1 percent of polyether modified silicone oil;

extreme pressure agent: zinc dialkyldithiophosphates; 3wt. -%)

And (3) bactericide: methylisothiazolone, 1wt.%;

pH regulators, Na₂CO₃Adjusting the pH value to 8-10;

the remainder was non-tap water, the hardness of water was <200ppm, oleic acid, boric acid and isopropanolamine were added as separate emulsions, and the complex ester a solution, labeled D-3, was not prepared.

Comparative example 4

A steel workpiece emulsion, the emulsion comprising:

compound ester: oleic isopropanolamine boronic acid complex ester, 10 wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.75 wt.%;

silicone nonionic surfactant: 0.1 percent of polyether modified silicone oil;

extreme pressure agent: zinc dialkyldithiophosphates; 3wt. -%)

pH value regulator: na (Na)₂CO₃Adjusting the pH value to 8-10;

the remainder was non-tap water, with a hardness of <200ppm of water, labeled D-4.

Example 1

An emulsion for fine machining of steel workpieces, the emulsion comprising:

refining mechanical composite base oil: is selected from the mixture of L-AN10 and sulfonated castor oil, and the mass ratio is 1: 0.2, 20 wt.%;

compound ester: oleic isopropanolamine boronic acid complex ester, 3wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.5 wt.%;

silicone nonionic surfactant: polyether modified silicone oil, 0.05 wt.%;

extreme pressure agent: zinc dialkyldithiophosphates or alkanoates of cyclohexanediols; 1wt.%;

and (3) bactericide: 1wt.% of one or more of methylisothiazolone, methylenebischlorophenol or methylenedimorpholine;

pH value regulator: NaOH or Na₂CO₃Adjusting the pH value to 8-10;

the rest is non-tap water, and the hardness of the water is less than 200 ppm;

the emulsificationThe preparation method of the liquid comprises the following steps: firstly, oleic acid, boric acid and isopropanolamine are mixed according to a molar ratio of 1: (1-2): (4-6) 140-155^oPerforming esterification reaction for 2-3 h under C, cooling, and standing to obtain a composite ester A solution; then weighing a certain proportion of refined machine oil and sulfonated castor oil, placing them into a reaction kettle, adding a proper quantity of composite ester A solution, and adding 60-80% of composite ester A solution^oC, slowly stirring for 1-2 h to obtain an oil phase B liquid which is uniformly mixed; then weighing the hardness<200ppm of non-tap water is put into a stirring reaction kettle, then sodium petroleum sulfonate and polyether modified silicone oil are added into the stirring reaction kettle, and the stirring reaction kettle is heated to 60 to 80 DEG^oC, stirring for 1-2 h to obtain a uniform solution C, then pouring the solution C into the solution B, mixing, and mixing 60-80%^oC, stirring for 0.5h under heat preservation to obtain uniform O/W emulsion, and then cooling to 40 DEG^oC, adding an extreme pressure agent and a bactericide, continuously stirring for 1-1.5 h, cooling to room temperature, and then using NaOH or Na₂CO₃And adjusting the pH value range of the emulsion to 8-10 to finally obtain the emulsion for processing the steel workpiece.

The treatment process of the used waste emulsion comprises the steps of firstly collecting the used waste emulsion in a collection box, separating solid steel scrap impurities and liquid through a centrifugal machine and a filter, and then adding 5wt.% of mixed liquid of sulfuric acid, hydrochloric acid and calcium chloride into the liquid, wherein the mass ratio of the sulfuric acid to the hydrochloric acid to the calcium chloride is 1: 0.5: (0.1-0.3), the pH value of the liquid is 6-7, so that the oil and the wastewater are separated, the obtained wastewater is treated by an active coal adsorption and electrocoagulator to remove redundant organic substances, the wastewater is purified, the oil content of the finally discharged wastewater is lower than 5mg/L, the suspended matter is lower than 300mg/L, the Chemical Oxygen Demand (COD) is lower than 80mg/L, and the obtained oil phase can be regenerated and recycled for the emulsion base oil for fine processing of steel workpieces.

Example 2

An emulsion for fine machining of steel workpieces, the emulsion comprising:

refining mechanical composite base oil: is selected from the mixture of L-AN15 and sulfonated castor oil, and the mass ratio is 1: 0.3, 40 wt.%;

compound ester: oleic isopropanolamine boronic acid complex ester, 10 wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.75 wt.%;

silicone nonionic surfactant: polyether modified silicone oil, 0.1 wt.%;

extreme pressure agent: zinc dialkyldithiophosphates; 3wt.%;

and (3) bactericide: methylisothiazolone, 1wt.%;

pH value regulator: na (Na)₂CO₃Adjusting the pH value to 8-1;

the rest is non-tap water, and the hardness of the water is less than 200 ppm; labeled S-1.

Example 3

An emulsion for fine machining of steel workpieces, the emulsion comprising:

refining mechanical composite base oil: the mixture of L-AN32 and sulfonated castor oil is prepared from the following components in a mass ratio of 1: 0.4, 65 wt.%;

compound ester: 15wt.% isopropanolamine oleic acid boronic acid complex ester;

anionic surfactant: sodium petroleum sulfonate, 1wt.%;

silicone nonionic surfactant: polyether modified silicone oil, 0.2 wt.%;

extreme pressure agent: alkanoic acid esters of cyclohexane diols; 5wt. -%)

And (3) bactericide: one or more of methylenedimorpholine, 2 wt.%;

pH value regulator: NaOH or Na₂CO₃Adjusting the pH value to 8-10;

the remainder was non-tap water, with water hardness <200 ppm.

Table 1 shows the results of the emulsion performance tests.

TABLE 1

Firstly, as for the emulsion, the base oil is the main component, closely related to the lubricity, the L-AN mechanical oil is prepared from refined mineral oil, usually, the mechanical equipment with light load and high rotating speed can select low-viscosity mechanical oil, and the equipment with heavy load and high rotating speed can select high-viscosity mechanical oil, but the adhesiveness, extreme pressure property and corrosion resistance of the L-AN mechanical oil are all required to be improved, for example, in D-1, when the base oil is only the mechanical oil L-AN, the friction coefficient of the L-AN mechanical oil is far higher than that of D-3, D-4 and S-1, therefore, the modified castor oil is added from the base oil, the modified castor oil is sulfonated oil generated by sulfonating the castor oil by sulfuric acid, the lubricity of the base oil can be obviously improved, namely, the friction coefficient of the L-1 is reduced, for example, under the condition of the same parameters, the friction coefficient of the D-1 is 0.068, and the friction coefficient of the S-, in addition, the modified castor oil has the advantages of improving the lubricity of the base oil and reducing the dosage of the base oil, and is also an excellent emulsifier, such as ricinoleic acid alkanolamide, undecylenic acid alkanolamide and the like which are recently appeared, which can improve the oil-water stability of the emulsion.

Secondly, polyol and fatty acid are usually added into the emulsion, wherein the polyol is generally used as an antirust agent or a stabilizer or a corrosion inhibitor, the fatty acid is used as an extreme pressure agent and is adsorbed with the metal surface to form a protective film, but if the polyol is added independently, the extreme pressure effect and the stabilizing effect are not mutually assisted and added, but are mutually influenced, the stability of an emulsified O/W system and the stability of a metal surface adsorption film are reduced, such as D-3 and S-1 are compared, but if the antirust agent and the extreme pressure agent are not added, the cutting effect is extremely poor, so that the oleic acid isopropanolamine boric acid composite ester is generated through the pre-esterification reaction of fatty acid oleic acid, inorganic acid boric acid and polyalcohol amine, the composite ester has a remarkable effect on the improvement of the stability and the antirust property of the emulsion, and for a mature emulsion system, for finely processed steel parts, the oleic acid isopropanolamine boric acid composite ester is not used for effectively generating a proper lubricating film on the surface of a base material. The action principle of the extreme pressure agent is that the extreme pressure antiwear agent is decomposed under friction and high temperature and reacts with metal to generate a compound with lower shearing stress and melting point than pure metal, so that the metal surface is effectively protected by preventing the occlusion and welding of the contact surface. The main current extreme pressure agents are the following: (1) a sulfur-based additive: the sulfur-containing additive is the most effective extreme pressure antiwear agent generally applied in the metal working fluid industry at present, and the sulfur or chlorine additive is mainly usedThe pyrolysis takes effect; (2) phosphorus-containing additives, which are earlier antiwear agents. The action mechanism is as follows: firstly adsorbing on the metal surface, hydrolyzing to generate acidic phosphate, forming organic metal phosphate on the metal surface, and finally, further hydrolyzing under the extreme pressure condition to generate an inorganic ferrous sulfate film which plays a role in extreme pressure wear resistance. (3) The most widely used chlorine-based additives and chlorine-based extreme pressure agents are aliphatic chlorides such as chlorinated paraffins and chlorinated fats. The action mechanism of the chlorine-containing extreme pressure antiwear agent is as follows: is heated to decompose to generate FeCl₂、FeCl₃And FeOCl and other ferric chloride films play roles in resisting abrasion and preventing sintering. (4) Boron is a relatively new type of antiwear element. The antiwear mechanism of action of boron is manifested by the formation of boric acid on the metal surface, which acts by deposition. However, the current advocated "environmentally friendly" products require (1) to be free of chlorine and nitrogen; (2) no heavy metal is contained; (3) low toxicity; (4) is biodegradable. The invention thus uses alkanoates of cyclohexanediols as extreme pressure agents, although parallel solutions have also been proposed using zinc dialkyldithiophosphates as extreme pressure agents, acting by adsorption and thermal decomposition.

Then, anionic surfactant petroleum sodium sulfonate and organosilicon nonionic surfactant polyether modified silicone oil are indispensable components in the emulsifier, and if no surfactant exists, an effective emulsion system cannot be generated.

The bactericide is very important for the service life of the emulsion, the emulsion contains a large amount of mineral oil, fatty acid soap, amine, sulfonate, water and other components, and is easily attacked by microorganisms, and the emulsion is rotten and deteriorated due to mass propagation of the microorganisms such as bacteria, fungi and the like in the water. Wherein, the anaerobic bacteria can reduce sulfate, release hydrogen sulfide gas and generate stink; the aerobic bacteria can generate organic acid and other corrosive metals, and mass propagation of the fungi can cause block generation, so that cooling liquid circulation pipelines and filter screens of machine tools are easily blocked. In addition, the water quality of the emulsion is also important for the emulsion system of the emulsion, and as shown in the table, the difference of water quality has obvious influence on the colony number, is easy to cause saponification, influences the stability of the O/W system,the pH value of the emulsion of the invention is alkaline, and the pH value is 8-10. Mainly considering bactericidal property and avoiding the phenomena of demulsification and oil-water separation caused by pH lower than 6 due to the occurrence of bacterial colonies, NaOH or Na is used₂CO₃As a modulator, in addition, the D-4 and S-1 data show that the presence of the biocide does not have a significant effect on the coefficient of friction.

The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims

1. The emulsion for fine machining of the steel workpiece is characterized by comprising the following components in percentage by mass:

compound ester: oleic isopropanolamine boronic acid complex ester, 3wt.%;

anionic surfactant: sodium petroleum sulfonate, 0.5 wt.%;

silicone nonionic surfactant: polyether modified silicone oil, 0.05 wt.%;

pH value regulator: NaOH or Na₂CO₃Adjusting the pH value to 8-10;

the rest is non-tap water, and the hardness of the water is less than 200 ppm;

the preparation method of the emulsion comprises the following steps: firstly, oleic acid, boric acid and isopropanolamine are mixed according to a molar ratio of 1: (1-2): (4-6) 140-155^oC, esterification reaction for 2-3 h, cooling and standingPlacing to obtain a composite ester A solution; then weighing a certain proportion of refined machine oil and sulfonated castor oil, placing them into a reaction kettle, adding a proper quantity of composite ester A solution, and adding 60-80% of composite ester A solution^oC, slowly stirring for 1-2 h to obtain an oil phase B liquid which is uniformly mixed; then weighing the hardness<200ppm of non-tap water is put into a stirring reaction kettle, then sodium petroleum sulfonate and polyether modified silicone oil are added into the stirring reaction kettle, and the stirring reaction kettle is heated to 60 to 80 DEG^oC, stirring for 1-2 h to obtain a uniform solution C, then pouring the solution C into the solution B, mixing, and mixing 60-80%^oC, stirring for 0.5h under heat preservation to obtain uniform O/W emulsion, and then cooling to 40 DEG^oC, adding an extreme pressure agent and a bactericide, continuously stirring for 1-1.5 h, cooling to room temperature, and then using NaOH or Na₂CO₃And adjusting the pH value range of the emulsion to be 8-10, and finally obtaining the emulsion for processing the steel workpiece, wherein the friction coefficient of the emulsion to the steel workpiece is 0.038.

2. The method of claim 1, wherein the emulsion is used waste emulsion, the used waste emulsion is collected in a collection box, solid steel scrap impurities and liquid are separated by a centrifuge and a filter, and then 5wt.% of mixed solution of sulfuric acid, hydrochloric acid and calcium chloride is added into the liquid, wherein the mass ratio of the sulfuric acid, the hydrochloric acid and the calcium chloride is 1: 0.5: (0.1-0.3), the pH value of the liquid is 6-7, so that the oil and the wastewater are separated, the obtained wastewater is treated by an active coal adsorption and electrocoagulator to remove redundant organic substances, the wastewater is purified, the oil content of the finally discharged wastewater is lower than 5mg/L, the suspended matter is lower than 300mg/L, and the chemical oxygen consumption is lower than 80mg/L, and the obtained oil phase can be regenerated and recycled for emulsion base oil for fine processing of steel workpieces.