CN111100768A

CN111100768A - Industrial heavy oil dirt cleaning agent and preparation method thereof

Info

Publication number: CN111100768A
Application number: CN201911392432.0A
Authority: CN
Inventors: 不公告发明人
Original assignee: Changsha Erdao New Energy Technology Co ltd
Current assignee: Changsha Erdao New Energy Technology Co ltd
Priority date: 2019-12-30
Filing date: 2019-12-30
Publication date: 2020-05-05

Abstract

The invention discloses an industrial heavy oil dirt cleaning agent, which comprises the following components: anionic surfactant, nonionic surfactant, polyethylene glycol, sodium metasilicate, triethylamine, terpene compound, inorganic base, emulsifier and water. The industrial heavy oil dirt cleaning agent has a remarkable removing effect on heavy oil dirt attached to equipment, particularly semisolid heavy oil dirt; the stability is excellent; and the industrial heavy oil dirt cleaning agent contains less organic solvents and is a low-toxicity solvent, so that no pressure is brought to the environment.

Description

Industrial heavy oil dirt cleaning agent and preparation method thereof

Technical Field

The invention belongs to the field of industrial cleaning, and particularly relates to a formula and a preparation method of an industrial heavy oil dirt cleaning agent.

Background

Industrial equipment accumulates a large amount of heavy oil stains in daily production and maintenance, and the heavy oil stains mainly comprise various cutting fluids, lubricating oil and grease for rust prevention which are remained in the processing process. Therefore, regular cleaning of industrial machinery is required. Industrial cleaning has been developed to date and has penetrated all industrial fields, such as machinery, textile printing and dyeing, petrochemical industry, mining and smelting, chemical industry, surface treatment, instruments and meters, electronics, semiconductors, clocks and watches, jewelry, biomedicine, electronic optics and other industries. The current cleaning agents are mainly divided into three types, namely water-based cleaning agents, solvent cleaning agents and semi-water-based cleaning agents.

The solvent cleaning agent mainly refers to an organic solvent type cleaning agent which contains no water or less water, and mainly comprises hydrocarbons, chlorohydrocarbons, bromohydrocarbon and alcohols. The solvent cleaning agent has the characteristics that the removal rate of organic dirt such as grease is ideal, the residual quantity of the surface is small after cleaning, but the solvent cleaning agent is a VOC substance, so that the solvent cleaning agent has serious toxic hazard and pollution to natural environments such as water, air and the like, and the solvent cleaning agent can completely exit the market in the near future along with the implementation of green environmental protection policies and the enhancement of environmental protection awareness of people in recent years.

The early water-based cleaning agent has single component, is mainly cleaned by a strong alkaline component, and has larger limitation; then gradually developing into water-soluble components, such as water-based cleaning agents compounded by ether, alcohol, salts and the like. Its advantages are no corrosion, no foam, low cost and less pollution, but its disadvantage is also obvious, and it has limited effect to clean greasy dirt, especially heavy oil dirt.

The current mainstream type cleaning agent is a semi-water-based cleaning agent, and the formula of the cleaning agent simultaneously contains a small amount of organic solvent, water and corresponding components. The semi-water-based cleaning agent has the cleaning capability of the solvent cleaning agent on oil stains, and also has the treatment capability and low toxicity of the water-based cleaning agent on inorganic dirt, so that the semi-water-based cleaning agent has a wider application range. However, the cleaning ability of the prior semi-water-based cleaning agent to the heavy oil dirt, especially to the semi-solid oil dirt at normal temperature or low temperature, is not ideal, which is a problem difficult to solve in many industrial cleaning fields.

Therefore, it is highly desirable to find a semi-aqueous cleaning agent that has the desired technical effect of removing heavy oil stains while retaining the advantages of aqueous cleaning agents.

Disclosure of Invention

Compared with the industrial heavy oil dirt cleaning agent in the comparative example provided by the invention, the industrial heavy oil dirt cleaning agent disclosed by the invention has a remarkable removal effect on heavy oil dirt attached to equipment, particularly semisolid heavy oil dirt; the stability is excellent; and the industrial heavy oil dirt cleaning agent contains less organic solvents and is a low-toxicity solvent, so that no pressure is brought to the environment.

The invention aims to provide an industrial heavy oil dirt cleaning agent, which is realized by the following technical means.

An industrial heavy oil dirt cleaning agent comprises the following components in parts by weight:

further, the terpene compound is a diterpene compound, a triterpene compound or a tetraterpene compound.

Further, the terpene compound contains at least one six-membered cyclic structure.

Further, the terpene compound is selected from one of the following structures:

further, the anionic surfactant is selected from one or more of LAS, AES, AEC, MES, SAS or AOS.

Further, the nonionic surfactant is selected from alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ethers, polyoxyethylene amides, alkylolamides or fatty acid-polyoxyethylene esters.

Further, the emulsifier is selected from span or tween emulsifiers.

The invention also aims to provide a preparation method of the industrial heavy oil dirt cleaning agent, which is realized by the following technical means.

The preparation method of the industrial heavy oil dirt cleaning agent comprises the following steps:

s1, adding the water in the claim 1 into a reaction kettle, then adding an anionic surfactant and a nonionic surfactant, then heating to 40-50 ℃, and stirring at the rotating speed of 450-650rpm for 10-30min to dissolve the components in the water;

s2, adding an emulsifier into the mixture to form a mixture;

s3, heating the mixture to 55-65 ℃, stirring at the rotating speed of 600-800rpm, and adding the terpene compound into the mixture in batches in the following manner:

(1) adding terpene compounds in two adjacent batches at a time interval of 15s-1 min;

(2) adding one batch of terpene compounds into the mixture, stirring until the mixture is clear, and adding the next batch of terpene compounds into the mixture;

s4, after the terpene compound is added, adding polyethylene glycol, sodium metasilicate, triethylamine and inorganic base, and stirring at the rotating speed of 600-800rpm for 10-30min at the temperature of 55-65 ℃.

Further, the preparation method of the industrial heavy oil dirt cleaning agent comprises the following steps:

s1, adding 100 parts by mass of water into a reaction kettle, adding 20 parts by mass of an anionic surfactant LAS and 10 parts by mass of a nonionic surfactant fatty alcohol-polyoxyethylene ether, heating to 40-50 ℃, and stirring at the rotating speed of 450-650rpm for 10-30min to dissolve the components in the water;

s2, adding 10 parts by mass of emulsifier Tween into the mixture to form a mixture;

s3, heating the mixture to 55-65 ℃, stirring at the rotating speed of 600-800rpm, and adding the terpene compound into the mixture in 7-10 batches in the following manner:

s4, after the terpene compound is added, adding polyethylene glycol, sodium metasilicate, triethylamine and inorganic base, and stirring at the rotating speed of 600-800rpm for 10-30min at the temperature of 55-65 ℃;

wherein the structural formula of the terpene compound added in the S3 is as follows:

the invention has the following beneficial effects:

(1) the industrial heavy oil dirt cleaning agent is prepared by adopting a method of compounding an anionic surfactant, a nonionic surfactant and a terpene compound. The surfactant, the nonionic surfactant and the terpene compound have a synergistic effect in the industrial heavy oil dirt cleaning agent, and the removal effect of the formula on the heavy oil dirt, particularly semisolid heavy oil dirt, is remarkably improved. This is due to:

it is known that anionic surfactants and nonionic surfactants have the effect of removing oil stains, however, the traditional anionic surfactants, nonionic surfactants or combination thereof generally have a remarkable effect of removing liquid oil stains, but since semisolid heavy oil stains generally have strong adhesion with bases, large density and small specific surface area, the surfactants are difficult to penetrate into the semisolid heavy oil stains, and the heavy oil stains are wetted, curled, solubilized and the like. The terpene compound is a well-known high-efficiency oil-soluble organic substance and has excellent affinity with semisolid heavy oil dirt. It has been surprisingly found that terpene compounds have better penetration and permeability to solid and semi-solid greases than polyols, so as to penetrate deeply into the semi-solid heavy oil scale and deeply wet it, thereby greatly increasing the specific surface area of wetting of the semi-solid heavy oil scale. Furthermore, especially the terpene compound with polyterpene and ring has excellent solubilization function for macromolecule anionic surfactant and nonionic surfactant, such as LAS and fatty alcohol polyoxyethylene ether, so that the surfactant can enter into the semi-solid heavy oil dirt together with the terpene compound, the surfactant can wet and curl the heavy oil dirt from the inside of the heavy oil dirt, the semi-solid structure is further broken down, the adhesion of the semi-solid heavy oil dirt and the substrate is reduced, and the large semi-solid heavy oil dirt is separated into small and even liquid grease, so that the contact area of the surfactant and the heavy oil dirt is further increased. It can be seen that, due to the terpene compounds, especially polyterpene and cyclic terpene compounds, the surfactant formed by compounding the anionic surfactant, such as LAS, AES, AEC or MES, and the nonionic surfactant, such as alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, polyoxyethylene amide, alkylolamide or fatty acid-polyoxyethylene ester, has excellent permeability and solubilization, so that the surfactant can effectively wet, crimp and solubilize the semi-solid heavy oil stains, thereby achieving the effect of efficiently removing the semi-solid heavy oil stains.

(2) The polyethylene glycol and the emulsifier in the industrial heavy oil dirt cleaning agent disclosed by the invention further enable the terpene compound to be more completely dispersed in the water phase, so that the compatibility and stability of each component in the formula are improved. The synergistic effect of the emulsifier and the surfactant, in turn, allows the terpene compound and the aqueous phase of the formulation to form a good and stable homogeneous phase and to maintain this ideal state over a prolonged period of time. Therefore, the formula is not easy to generate the phenomenon of layering or precipitation along with the change of the external environment, so that the decontamination effect can be maintained for a long time.

(3) The terpene compound is mostly derived from natural product extracts, contains a large amount of double bonds, is non-toxic and easy to degrade, and completely accords with the current green and environment-friendly policy trend and the mainstream thought of people.

Detailed Description

The invention is further illustrated by the following description and specific examples, which are not intended to limit the invention in any way. The methods and apparatus employed in the present invention are conventional in the art, unless otherwise indicated.

Example 1

the terpene compound is selected from the following structures:

s1, adding 70 parts by mass of water into a reaction kettle, adding 10 parts by mass of an anionic surfactant LAS and 5 parts by mass of a nonionic surfactant fatty alcohol-polyoxyethylene ether, heating to 40 ℃, and stirring at a rotating speed of 450rpm for 10min to dissolve the components in the water;

s2, adding 4 parts by mass of emulsifier Tween-20 into the mixture to form a mixture;

s3, heating the mixture to 55 ℃, stirring at the rotating speed of 600rpm, and adding 6 parts by weight of the terpene compound with the structure into the mixture in batches in the following manner:

(1) adding terpene compounds in two adjacent batches at a time interval of 1 min;

s4, after the terpene compound is added, 1 part by mass of polyethylene glycol, 0.5 part by mass of sodium metasilicate, 3 parts by mass of triethylamine and 2 parts by mass of potassium hydroxide are added into the terpene compound, and the mixture is stirred at the rotating speed of 600rpm for 10min at the temperature of 55 ℃.

Finally obtaining the industrial heavy oil dirt cleaning agent.

Example 2

the terpene compound is selected from the following structures:

s1, adding 100 parts by mass of water into a reaction kettle, then adding 20 parts by mass of anionic surfactant AES and 10 parts by mass of nonionic surfactant polyoxyethylene amide, heating to 50 ℃, and stirring at a rotating speed of 650rpm for 30min to dissolve the components in the water;

s2, adding 10 parts by mass of emulsifier Tween-80 into the mixture to form a mixture;

s3, heating the mixture to 65 ℃, stirring at the rotating speed of 800rpm, and adding 12 parts by weight of the terpene compound with the structure into the mixture in batches in the following manner:

(1) the time interval between the addition of two adjacent batches of terpene compounds is 15 s;

s4, after the terpene compound is added, adding 3 parts by weight of polyethylene glycol, 1 part by weight of sodium metasilicate, 6 parts by weight of triethylamine and 5 parts by weight of potassium carbonate, and stirring at the rotating speed of 800rpm for 30min at 65 ℃.

Finally obtaining the industrial heavy oil dirt cleaning agent.

Example 3

the terpene compound is selected from the following structures:

s1, adding 80 parts by mass of water into a reaction kettle, adding 15 parts by mass of anionic surfactant AEC and 7 parts by mass of nonionic surfactant dodecyl diethanolamide, heating to 45 ℃, and stirring at the rotating speed of 550rpm for 20min to dissolve the components in the water;

s2, adding 7 parts by mass of emulsifier span-80 into the mixture to form a mixture;

s3, heating the mixture to 60 ℃, stirring at the rotating speed of 700rpm, and adding 10 parts by weight of the terpene compound with the structure into the mixture in batches, wherein the batch adding mode is as follows:

(1) the time interval between the addition of two adjacent batches of terpene compounds is 45 s;

s4, after the terpene compound is added, 2 parts by weight of polyethylene glycol, 0.7 part by weight of sodium metasilicate, 4 parts by weight of triethylamine and 3 parts by weight of sodium carbonate are added into the terpene compound, and the mixture is stirred for 20min at the rotating speed of 700rpm at the temperature of 60 ℃.

Finally obtaining the industrial heavy oil dirt cleaning agent.

Example 4

the terpene compound is selected from the following structures:

s1, adding 80 parts by mass of water into a reaction kettle, adding 15 parts by mass of anionic surfactant AEC and 7 parts by mass of nonionic surfactant dodecyl diethanolamide, heating to 43 ℃, and stirring at the rotating speed of 520rpm for 25min to dissolve the components in the water;

s2, adding 6 parts by mass of Tween-20 into the mixture to form a mixture;

s3, heating the mixture to 62 ℃, stirring at the rotating speed of 730rpm, and adding 8 parts by weight of the terpene compound with the structure into the mixture in batches, wherein the batch adding mode is as follows:

(1) the time interval between the addition of two adjacent batches of terpene compounds is 55 s;

s4, after the terpene compound is added, 1.5 parts by weight of polyethylene glycol, 0.6 part by weight of sodium metasilicate, 5 parts by weight of triethylamine and 4 parts by weight of sodium hydroxide are added into the terpene compound, and the mixture is stirred at the rotating speed of 720rpm for 25min at the temperature of 62 ℃.

Finally obtaining the industrial heavy oil dirt cleaning agent.

Comparative example 1

The components and the preparation method of the industrial heavy oil dirt cleaning agent are the same as those of the industrial heavy oil dirt cleaning agent described in the example 1, and the only difference is that the industrial heavy oil dirt cleaning agent of the comparative example 1 does not contain the terpene compound described in the example 1, but replaces the terpene compound by 8 parts by mass of polyethylene glycol.

Comparative example 2

The same components and preparation method as those of the industrial heavy oil dirt cleaning agent described in example 1 are adopted, and the only difference is that the industrial heavy oil dirt cleaning agent of comparative example 2 does not contain the terpene compound described in example 1, but is replaced by 8 parts by mass of glycerol.

Comparative example 3

The same components and preparation method as those of the industrial heavy oil dirt cleaning agent described in example 1 are adopted, and the only difference is that the industrial heavy oil dirt cleaning agent of comparative example 3 does not contain the terpene compound described in example 1, but substitutes the monoterpene compound menthol with 8 parts by mass.

Comparative example 4

The same components and preparation method as those of the industrial heavy oil dirt cleaning agent described in example 1 are adopted, and the only difference is that the industrial heavy oil dirt cleaning agent of the comparative example 3 does not contain the terpene compound described in example 1, but replaces the monoterpene compound limonene with the mass part of 8 parts.

Comparative example 5

The same components and preparation method as those of the industrial heavy oil dirt cleaning agent described in example 1 are adopted, and the only difference is that the industrial heavy oil dirt cleaning agent of comparative example 3 does not contain the terpene compound described in example 1, but replaces the monoterpene compound perillyl alcohol with the mass part of 8 parts.

Example 5

The heavy oil stain removing effects of the heavy oil stain cleaners described in examples 1 to 4 and comparative examples 1 to 5 were tested. The test method is as follows:

(1) preparing dirt: mixing lard oil: vegetable oil: carbon black: egg white was mixed 1:1:1:1 to form a liquid mixture.

(2) Sample preparation: cutting a stainless steel plate into a plurality of rectangular blocks of 20cm multiplied by 10cm, and recording the weight M1 of each plate one by one; then, the above liquid mixtures were uniformly coated on rectangular stainless steel plates, respectively, and the weight of the liquid dirt was about 10 g/plate.

(3) Sample post-treatment: the stainless steel sheet coated with the liquid dirt was subjected to the following treatment: firstly, putting a stainless steel plate into a 30 ℃ oven for aging for 24h, then taking out the stainless steel plate, and putting the stainless steel plate into a refrigerator for freezing for 24 h; the above procedure was repeated two more times to finally obtain stainless steel plates coated with heavy oil stains, and the weight M2 of each plate was recorded one by one.

(4) Stain removal test: and (3) placing the rectangular stainless steel plate treated in the step (A) on a horizontal desktop. The heavy oil stain cleaners described in examples 1-4 and comparative examples 1-5 were divided into seven groups, each group corresponding to one rectangular stainless steel plate. At 25 ℃, 20g of the heavy oil dirt cleaning agent is respectively taken and coated on a rectangular stainless steel plate, and then the stainless steel plate is kept stand for 30 min. Finally, the rectangular stainless steel plates were rinsed with clean water, and the weight M3 of each plate was recorded one by one, and the results are shown in Table 1

Calculating by the formula: the detergency ratio was 1- [ (M3-M1)/(M2-M1) ] × 100%.

TABLE 1 data relating to examples 1-4 and comparative examples 1-5

As can be seen from the above table, the examples 1-4 have the synergistic effect of the surfactant, the nonionic surfactant and the terpene compound, so that the removal rate of the semi-solid heavy oil dirt is more ideal and reaches more than 60%; compared with the comparative examples 1-2, the terpene compound is not contained, and the alcohols are used for replacing, so that the removal rate is not ideal, which shows that the alcohols do not have the function of deeply disintegrating the semi-solid heavy oil dirt by the terpene compound and the surfactant; in comparative examples 3 to 5, where the polyterpene compound was replaced with an equal mass fraction of the monoterpene compound, the ability to remove the semisolid heavy oil stains was somewhat lowered because the monoterpene compound had a limited solubilizing ability for the surfactant and thus the semisolid heavy oil stains could not be completely disrupted.

Example 6

To test the stability of the formulations of examples 1-4, comparative examples 1-5, the inventors employed the following test methods: 500g of each of the above 9 formulations was taken, filled in transparent PE bottles and sealed as samples. Putting the 9 samples into a 40 ℃ oven for 48h, and then putting the samples into a 0 ℃ refrigerator for 48 h; the above steps are cycled for three times. The sample was then removed and observed for appearance after standing, and the results are shown in table 2.

TABLE 2 appearance test results of examples 1 to 4 and comparative examples 1 to 5

	Appearance description
		Example 1	The appearance is homogeneous and slightly turbid
Example 2	The appearance is homogeneous and slightly turbid
		Example 3	The appearance is homogeneous and medium turbid
Example 4	The appearance is homogeneous and slightly turbid
		Comparative example 1	The appearance is layered, the supernatant is clear liquid, and the lower layer is a large amount of white flocculent solid
Comparative example 2	The appearance is layered, the supernatant is clear liquid, and the lower layer is a large amount of white flocculent solid
		Comparative example 3	The appearance is homogeneous and the color is severely turbid
Comparative example 4	The appearance is homogeneous, and a small amount of white precipitate is at the bottom of the bottle
		Comparative example 5	The appearance is homogeneous, and a small amount of white precipitate is at the bottom of the bottle

As can be seen from table 2, examples 1-4 exhibited excellent stability in the stability tested samples, and the samples remained homogeneous after multiple freeze-thaw cycles; however, the stability of the comparative examples 1-2 is poor, and a large amount of white flocculent solids are separated out from the bottom of the bottle, which proves that the compatibility of the components in the formula is poor; in contrast to comparative examples 3-5, monoterpene compounds have a certain solubilizing effect on the formulation and therefore have a positive effect on stability, but are still not as significant as polyterpene compounds have on the formulation ingredients.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The industrial heavy oil dirt cleaning agent as claimed in claim 1, wherein the cleaning agent comprises the following components in parts by mass:

2. the industrial heavy oil stain cleaner as claimed in claim 1, wherein the terpene compound is a diterpene compound, a triterpene compound or a tetraterpene compound.

3. The industrial heavy oil stain cleaner of claim 1, wherein the terpene compound contains at least one six-membered cyclic structure.

4. The industrial heavy oil stain cleaner of claim 1, wherein the terpene compound is selected from one of the following structures:

5. the industrial heavy oil scale cleaning agent according to claim 1, wherein the anionic surfactant is selected from one or more of LAS, AES, AEC or MES.

6. The industrial heavy oil dirt cleaning agent according to claim 1, wherein the nonionic surfactant is selected from alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ethers, polyoxyethylene amides, alkylolamides and fatty acid-polyoxyethylene esters.

7. The industrial heavy oil dirt cleaning agent according to claim 1, wherein the emulsifier is selected from span or tween emulsifiers.

8. The method for preparing the industrial heavy oil dirt cleaning agent as claimed in any one of claims 1 to 7, is characterized by comprising the following steps:

s2, adding an emulsifier into the mixture to form a mixture;

9. The preparation method of the industrial heavy oil dirt cleaning agent as claimed in claim 8, characterized by comprising the following steps: