WO2017111426A1 - Polymer scale cleaning liquid and polymer scale cleaning method using same - Google Patents

Abstract

Disclosed are a polymer scale cleaning liquid and a polymer scale cleaning method using the same, by which a surface having an emulsion-polymerized polymer scale attached thereto can be cleaned while minimizing environment pollution and without harm to a human body. The polymer scale cleaning method comprises a step for providing a water solution containing styrene to a surface to which an emulsion-polymerized polymer scale is attached, and removing the emulsion-polymerized polymer scale from the surface.

Description

Polymer scale washing liquid and polymer scale washing method using the same

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0184213 dated December 22, 2015, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

The present invention relates to a polymer scale washing solution and a method for washing the polymer scale using the same, and more particularly, to the surface on which the emulsion polymerized polymer scale is attached, which is harmless to the human body and can be cleaned while minimizing environmental pollution, and It relates to a polymer scale washing method using the same.

In general, a water jet injection method or a cleaning method using a strong cleaning chemical has been mainly used to clean a device such as a polymer polymerization reactor or a heat exchanger necessary for a subsequent process. However, in order to clean the reactor through water jet injection, not only it takes a lot of time because the operator has to enter the reactor and work directly after opening the reactor, and toxic substances may remain in the reactor. May cause a safety problem. In addition, the cleaning method using chemicals may also cause a safety situation for the operator, and there is a possibility of environmental pollution.

As discussed above, cleaning methods commonly used for cleaning polymer processing devices contain a number of elements that may be harmful to the human body or pollute the environment. Development of the method is required.

Accordingly, an object of the present invention for solving this problem is to provide a polymer scale washing liquid and a polymer scale washing method using the same, which can be harmless to the human body and can minimize environmental pollution, as well as shorten the time required for washing. will be.

In order to achieve the above object, the present invention, by supplying an aqueous solution containing styrene to the surface attached to the emulsion polymerization polymer scale, removing the emulsion polymerization polymer scale from the surface; washing the polymer scale comprising a Provide a method.

In addition, the present invention, water; And 0.1 to 100 parts by weight of styrene based on 100 parts by weight of water.

According to the polymer scale washing liquid and the method for washing the polymer scale using the same, when washing the surface on which the emulsion polymer scale is attached, it is not only harmless to the human body and minimizes environmental pollution, but also the time required for washing. It can be shortened.

1 is a photograph showing the state when the SBR scale in water for 1 hour at room temperature.

Figure 2 is a photograph comparing the appearance before and after washing the polymer processor by the polymer scale washing method according to the present invention.

3 is a view immediately after feeding the glass containers (A, B) to which the solid-state SBR specimen is attached, and an aqueous styrene solution or styrene.

4 is a view after 1 hour has passed after supplying an aqueous styrene solution or styrene to a glass container to which a solid SBR specimen is attached.

FIG. 5 is a view after 15 hours have passed after supplying an aqueous styrene solution or styrene to a glass container having a solid SBR specimen attached thereto.

Hereinafter, the present invention will be described in detail.

The polymer scale washing method according to the present invention includes supplying an aqueous solution containing styrene to a surface to which an emulsion polymer scale is attached, and removing the emulsion polymer scale from the surface.

The emulsion polymerization polymer scale is any one selected from the group consisting of a polymerization reactor in which a polymer emulsion polymerization reaction is performed or a heat exchanger, a storage device, a monomer separation device, and a transfer pipe in which processes after the reaction proceed. (I.e., foreign matter adhering to or sticking to the inner or outer surface of any one of the polymer processors), having a rubbery property to adhere to the surface, and having a lower density than water, and furthermore, the styrene Dissolves in an aqueous solution containing, for example, styrene butadiene rubber (SBR) scale, acrylonitrile butadiene styrene (ABS) scale and styrene butadiene latex (Styrene butadiene latex (SBL) scale and the like.

On the other hand, the material of the surface may be stainless steel (Steel use stainless, SUS) or glass (glass) corresponding to the various types of polymer processor material, the surface of the emulsion polymerization polymer scale with the styrene aqueous solution of the present invention Any material can be used as long as it can be separated from.

Generally, latex is an intermediate product prepared by supplying a raw material, an emulsifier and an initiator to a large amount of water during emulsion polymerization. The latex is removed by removing water, unreacted raw materials and emulsifiers from the prepared latex. Emulsion polymerization polymers, such as styrene butadiene rubber (SBR), which is a synthetic rubber product, are produced. Therefore, the emulsion polymerization polymer latex produced by the emulsion polymerization contains a large amount of water at a level of about 50 to 75% by mass.

Since the styrene butadiene rubber (SBR) includes butadiene (Butadiene), the SBR has the properties of the rubber, for this reason, the SBR is attached to the inner wall surface of the polymer processor such as a reactor or a heat exchanger Even if scratched, it forms a scale that does not fall well. In addition, since the SBR scale attached to the inner surface of the polymer processor is smaller in density than water, when the SBR scale is removed from the inner wall of the polymer processor and placed in pure water, the SBR scale floats in water. The SBR scale is not soluble in water. 1 is a photograph showing the case when the SBR scale in water for 1 hour at room temperature, in the case of A in which the SBR scale is placed in pure water, as described above, because the SBR scale is less dense than the water, It floats in water, and it can be seen that it does not dissolve in water and maintains a nearly circular shape over time. In addition, in the case of B which has been stirted after placing the SBR scale in pure water, the SBR scale is also insoluble in water (it is a magnetic bar that has sunk to the bottom).

According to the present invention, the polymer scale washing method according to the present invention utilizes the characteristics of the emulsion polymerization polymer scale such as the SBR scale as described above. When supplied to the surface surface, the emulsion-polymerized polymer scale absorbing the styrene aqueous solution is swelled to change into a sticky viscous state, and is separated from the surface by the buoyancy of water to separate the styrene. The emulsion polymerization polymer scale may be removed by dissolving the styrene solution in which the emulsion polymerization polymer scale is dissolved in an aqueous solution.

Figure 2 is a photograph comparing before and after the washing of the polymer processor by the polymer scale washing method according to the present invention, A and B of Figure 2 is before washing, C and D of Figure 2 is after washing. That is, before washing (A, B) it can be seen that a large amount of white SBR scale is attached to the inner surface of the processor such as the bottom surface or wall surface, but after washing with styrene solution (C, D) the SBR scale It can be seen that almost all of the polymer processor was removed.

On the other hand, the styrene aqueous solution is supplied by a method selected from the group consisting of a shedding (flowing) method, immersion method and jet injection method, in addition to the above methods, the styrene on the surface attached to the emulsion polymer scale By supplying an aqueous solution of lene, a method capable of separating and dissolving the surface of the emulsion polymerized polymer scale may be used without limitation. However, since the emulsion polymerization polymer scale is easily separated from the surface as the swelling time in the styrene aqueous solution becomes longer (see Examples below), the emulsion polymerization polymer scale is present in the styrene aqueous solution. In order to increase the time, it is preferable that the emulsion polymerized polymer scale is immersed in the styrene aqueous solution after the styrene aqueous solution is supplied, even when using any of the above feeding methods.

The content of styrene in the aqueous solution may be 0.1 to 99% by weight, preferably 0.1 to 50% by weight, more preferably 0.5 to 5% by weight, and most preferably 0.5 to 1% by weight, based on the total weight of the aqueous solution. . When the content of styrene in the aqueous solution is less than 0.1% by weight based on the total weight of the aqueous solution, dissolution of the emulsion polymerized polymer scale by the styrene aqueous solution may be insufficient, and when it exceeds 99% by weight, the buoyancy effect by water And no desorption of the emulsion polymerized polymer scale occurs. On the other hand, the emulsion polymerization polymer scale, depending on the content of the styrene contained in the aqueous solution, may be completely removed from the surface or remain a small amount on the surface.

On the other hand, the polymer scale washing method according to the present invention, by using a means selected from the group consisting of a brush (brush) and scraping (Scraping), to further remove the residual emulsion polymerization polymer scale not removed from the surface It may further comprise a step. That is, even with the polymer scale washing method according to the present invention, since it takes a long time to completely remove the emulsion-polymerized polymer scale from the adhesion corresponding surface (surface), if there is a time limit or a small amount of residual The above means can be used for this. In addition, in order to more quickly separate and remove the emulsion polymer scale from the surface, if necessary, it may further include a step of stirring after supplying a styrene solution.

Next, the polymer scale washing liquid according to the present invention is used to be supplied to the surface to which the emulsion polymerized polymer scale is attached, and is 0.1 to 99% by weight, preferably 0.1 to 50% by weight, based on water and the total weight. , More preferably 0.5 to 5% by weight, most preferably 0.5 to 1% by weight of styrene. On the other hand, the detailed description related to the polymer scale washing liquid according to the present invention, the contents described in the polymer scale washing method.

As described above, using the polymer scale washing liquid and the polymer scale washing method using the same according to the present invention, since the operator does not have to enter the inside of the polymer processor directly, it is harmless to the human body, and only a small amount of styrene is used as the washing liquid. Because of the use, it is environmentally friendly compared to the use of powerful cleaning chemicals, which can minimize environmental pollution and shorten the time required for cleaning.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. Naturally, such changes and modifications fall within the scope of the appended claims.

Example

Solubility Assessment of Styrene Butadiene Rubber (SBR) Scale-A. Immediately after Solvent Supply

Example 1

3 is a view immediately after supplying the glass containers (A, B) to which the solid-state SBR specimen is attached and styrene aqueous solution or styrene. First, 50 g of styrene butadiene rubber latex (SBR Latex) is used. vial), and dried in an oven at 65-70 ° C. to prepare solid SBR specimens to be used as scale, as shown in FIGS. 3A and 3B. Subsequently, as shown in FIG. 3C, an aqueous styrene solution (solvent) containing less than 1 ml of styrene (SM) and 99 ml of water is added to a vial to which the SBR specimen is attached, and at a rate of 100 rpm at room temperature. Stirred.

Example 2

As shown in D of FIG. 3, except that instead of using an aqueous styrene solution containing less than 1 ml of styrene and 99 ml of water, an aqueous styrene solution containing 5 ml of styrene and 95 ml of water is used. It carried out similarly to Example 1.

Example 3

As shown in E of FIG. 3, except that an aqueous styrene solution containing 50 ml of styrene and 50 ml of water is used instead of an aqueous styrene solution containing less than 1 ml of styrene and 99 ml of water. It carried out similarly to Example 1.

Comparative Example 1

As in F of FIG. 3, 100 ml of styrene was used instead of an aqueous styrene solution containing less than 1 ml of styrene and 99 ml of water, and was performed in the same manner as in Example 1.

As shown in FIG. 3, in the case of Examples 1 to 3 using the styrene aqueous solution immediately after supplying the solvent, the SBR specimen started to dissolve and the solution became cloudy, but only styrene was used as the solvent. In the case of Comparative Example 1, it can be seen that the SBR specimen remains intact.

EXAMPLES 1-3, COMPARATIVE EXAMPLE 1 Solubility Evaluation of Styrene Butadiene Rubber ( SBR ) Scale-B. 1 Hour After Solvent Supply

4 is a view after one hour has elapsed after supplying a styrene aqueous solution or styrene to a glass container with a solid SBR specimen attached, Figures A and B in Example 1, Examples in order from the left 2, Example 3 and Comparative Example 1 showing the container, Figure 4 B is the inverted container, Figure 4 C is a clockwise direction from the upper left, Example 1, Example 2, Example 3 and comparison Photo shows the bottom of the container of Example 1. As shown in FIG. 4, in the case of Comparative Example 1 (using 100 ml of styrene solvent), a large amount of SBR specimen (or SBR scale) remained almost intact even after 1 hour of solvent supply. In Examples 1 to 3 (using styrene aqueous solution), it can be seen that a significant amount of SBR specimens dissolved in 1 hour regardless of the styrene content in the aqueous solution.

Examples 1-3, Comparative Example 1 Solubility Evaluation of Styrene Butadiene Rubber ( SBR ) Scale-C. 15 Hours After Solvent Supply

FIG. 5 is a view after 15 hours have elapsed after supplying a styrene aqueous solution or styrene to a glass container to which a solid SBR specimen is attached. FIG. 2, Example 3 and Comparative Example 1 showing the container, Figure 5 B is the inverted container, Figure 5 C is a clockwise direction from the upper left, Example 1, Example 2, Example 3 and comparison Photo shows the bottom of the container of Example 1. As shown in FIG. 5, in the case of Comparative Example 1 (using 100 ml of styrene solvent), the SBR specimen attached to the bottom of the container was partially separated when 15 hours passed after the solvent supply, but a large change was observed. In the case of Examples 1 to 3 (using styrene aqueous solution), all of the SBR specimens attached to the bottom of the container were dissolved in 15 hours regardless of the styrene content in the aqueous solution, and only some of the specimens were in solution. You can see that it is floating on.

Claims (11)

Supplying an aqueous solution containing styrene to the surface to which the emulsion polymer scale is attached, and removing the emulsion polymer scale from the surface. The method of claim 1, wherein the emulsion polymerized polymer scale is selected from the group consisting of styrene butadiene rubber (SBR) scale, acrylonitrile butadiene styrene (ABS) scale and styrene butadiene latex (SBL) scale. , Polymer scale washing method. The method according to claim 1, wherein when the aqueous solution containing the styrene is supplied to the surface to which the polymer scale is attached, the emulsion-polymerized polymer scale absorbing the styrene solution is swelled to change into a viscous state, The polymer scale washing method, characterized in that separated from the surface by buoyancy of water. The method according to claim 3, wherein when the emulsion polymer scale is separated from the surface, the emulsion polymer scale is dissolved in the styrene aqueous solution. The method according to claim 1, wherein the surface is any one inner or outer surface selected from the group consisting of a polymerization reactor, a heat exchanger, a storage device, a monomer separation device and a transfer piping. The method of claim 1, wherein the styrene aqueous solution is supplied by a method selected from the group consisting of a shedding method, an immersion method, and a jet spray method. The method of claim 1, wherein the polymer scale cleaning method further comprises the step of further removing the residual emulsion polymer scale that has not been removed from the surface by means selected from the group consisting of brush and scraping. To the polymer scale washing method comprising a. The method of claim 1, wherein the content of styrene in the aqueous solution is 0.1 to 99 wt% based on the total weight of the aqueous solution. The method of claim 1, wherein the emulsion polymerized polymer scale is completely removed from the surface or remains in a small amount in accordance with the amount of styrene contained in the aqueous solution. water; And 0.1 to 99% by weight of styrene relative to the total weight; polymer scale washing liquid comprising. The polymer scale wash solution according to claim 10, wherein the wash liquid is supplied to and used on a surface to which the emulsion polymer scale is attached.

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