WO2017111426A1 - Liquide de nettoyage d'incrustations polymères et procédé de nettoyage d'incrustations polymères l'utilisant - Google Patents

Liquide de nettoyage d'incrustations polymères et procédé de nettoyage d'incrustations polymères l'utilisant Download PDF

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Publication number
WO2017111426A1
WO2017111426A1 PCT/KR2016/014927 KR2016014927W WO2017111426A1 WO 2017111426 A1 WO2017111426 A1 WO 2017111426A1 KR 2016014927 W KR2016014927 W KR 2016014927W WO 2017111426 A1 WO2017111426 A1 WO 2017111426A1
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WO
WIPO (PCT)
Prior art keywords
polymer scale
styrene
scale
aqueous solution
emulsion
Prior art date
Application number
PCT/KR2016/014927
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English (en)
Korean (ko)
Inventor
신대영
주은정
허창회
장성근
신준호
Original Assignee
주식회사 엘지화학
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Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Publication of WO2017111426A1 publication Critical patent/WO2017111426A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents

Definitions

  • 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.
  • 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.
  • a device such as a polymer polymerization reactor or a heat exchanger necessary for a subsequent process.
  • a cleaning method using chemicals may also cause a safety situation for the operator, and there is a possibility of environmental pollution.
  • 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.
  • 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.
  • 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.
  • the present invention water; And 0.1 to 100 parts by weight of styrene based on 100 parts by weight of water.
  • 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.
  • FIG 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.
  • FIG. 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.
  • the polymer scale washing method 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.
  • SBR styrene butadiene rubber
  • ABS acrylonitrile butadiene styrene
  • SBL styrene butadiene latex
  • 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.
  • 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.
  • the SBR styrene butadiene rubber
  • 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.
  • 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.
  • FIG. 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.
  • the SBR scale is also insoluble in water (it is a magnetic bar that has sunk to the bottom).
  • the polymer scale washing method utilizes the characteristics of the emulsion polymerization polymer scale such as the SBR scale as described above.
  • 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.
  • 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
  • a method capable of separating and dissolving the surface of the emulsion polymerized polymer scale may be used without limitation.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • the detailed description related to the polymer scale washing liquid according to the present invention the contents described in the polymer scale washing method.
  • 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.
  • FIG. 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.
  • SBR Latex styrene butadiene rubber latex
  • vial 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.
  • 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.
  • FIG. 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.
  • 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.
  • Examples 1 to 3 using styrene aqueous solution
  • 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.
  • 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.

Abstract

La présente invention concerne un liquide de nettoyage d'incrustations polymères et un procédé de nettoyage d'incrustations polymères l'utilisant, grâce auxquels une surface sur laquelle des incrustations polymères polymérisées en émulsion sont fixées peut être nettoyée tout en réduisant la pollution de l'environnement et sans nuire au corps humain. Le procédé de nettoyage d'incrustations polymères comprend une étape consistant à amener une solution aqueuse contenant du styrène sur une surface sur laquelle des incrustations polymères polymérisées en émulsion sont fixées et à éliminer les incrustations polymères polymérisées en émulsion de la surface.
PCT/KR2016/014927 2015-12-22 2016-12-20 Liquide de nettoyage d'incrustations polymères et procédé de nettoyage d'incrustations polymères l'utilisant WO2017111426A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0184213 2015-12-22
KR20150184213 2015-12-22

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WO2017111426A1 true WO2017111426A1 (fr) 2017-06-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR940001062B1 (ko) * 1986-06-06 1994-02-12 가네가후치 가가꾸 고교 가부시끼가이샤 중합반응기 내부의 세척방법
KR19980086890A (ko) * 1997-05-09 1998-12-05 버클리 가이 줄리안 스케일 제거제
KR20020000796A (ko) * 1999-03-26 2002-01-05 추후 녹 및 스케일 제거용 조성물 및 방법
KR101350687B1 (ko) * 2010-06-30 2014-01-13 주식회사 엘지화학 고분자 라텍스로부터 제조된 슬러리의 잔류 모노머 제거방법
KR101553917B1 (ko) * 2010-08-13 2015-09-17 퍼블릭 조인트 스톡 컴퍼니 “시부르 홀딩” 중합 장치로부터 고분자량의 폴리머인 약용해성 퇴적물을 제거하는 방법(여러 구현예들)

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR940001062B1 (ko) * 1986-06-06 1994-02-12 가네가후치 가가꾸 고교 가부시끼가이샤 중합반응기 내부의 세척방법
KR19980086890A (ko) * 1997-05-09 1998-12-05 버클리 가이 줄리안 스케일 제거제
KR20020000796A (ko) * 1999-03-26 2002-01-05 추후 녹 및 스케일 제거용 조성물 및 방법
KR101350687B1 (ko) * 2010-06-30 2014-01-13 주식회사 엘지화학 고분자 라텍스로부터 제조된 슬러리의 잔류 모노머 제거방법
KR101553917B1 (ko) * 2010-08-13 2015-09-17 퍼블릭 조인트 스톡 컴퍼니 “시부르 홀딩” 중합 장치로부터 고분자량의 폴리머인 약용해성 퇴적물을 제거하는 방법(여러 구현예들)

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