JPH09157324A - Method for storing recovered unreacted vinyl chloride monomer - Google Patents
Method for storing recovered unreacted vinyl chloride monomerInfo
- Publication number
- JPH09157324A JPH09157324A JP7337898A JP33789895A JPH09157324A JP H09157324 A JPH09157324 A JP H09157324A JP 7337898 A JP7337898 A JP 7337898A JP 33789895 A JP33789895 A JP 33789895A JP H09157324 A JPH09157324 A JP H09157324A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride monomer
- tank
- recovered
- unreacted vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000000178 monomer Substances 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 34
- 238000004821 distillation Methods 0.000 claims abstract description 33
- 239000003112 inhibitor Substances 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 51
- 238000003860 storage Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 32
- 239000007788 liquid Substances 0.000 description 47
- 238000011084 recovery Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002954 polymerization reaction product Substances 0.000 description 9
- 230000003405 preventing effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 C 4 hydrocarbons Chemical class 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル重合体
の製造工程において、重合反応停止後に回収される未反
応塩化ビニルモノマーを貯蔵する方法に関する。TECHNICAL FIELD The present invention relates to a method for storing unreacted vinyl chloride monomer recovered after termination of a polymerization reaction in a process for producing a vinyl chloride polymer.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
塩化ビニル重合体の製造工程において、重合反応停止後
に未反応塩化ビニルモノマーを回収し、更に回収した未
反応塩化ビニルモノマーに含有される高沸点不純物を除
去して回収未反応塩化ビニルモノマーを再利用してい
る。2. Description of the Related Art
In the production process of vinyl chloride polymer, unreacted vinyl chloride monomer is recovered after termination of the polymerization reaction, and high boiling impurities contained in the recovered unreacted vinyl chloride monomer are removed to reuse the recovered unreacted vinyl chloride monomer. doing.
【０００３】重合反応停止後の回収未反応塩化ビニルモ
ノマーの回収工程について図１により説明すると、重合
反応停止後、重合器内、スラリータンク内等より未反応
塩化ビニルモノマーガス回収配管を通じて回収未反応塩
化ビニルモノマーガスを回収する。The recovery process of the unreacted vinyl chloride monomer recovered after the termination of the polymerization reaction will be described with reference to FIG. Collect vinyl chloride monomer gas.
【０００４】回収された未反応塩化ビニルモノマーガス
は、液化工程（１）を経て液化され、粗ＶＣタンク
（２）に貯蔵される。粗ＶＣタンク（２）に貯蔵された
回収未反応塩化ビニルモノマー液は蒸留精製工程（３）
に通されて精製される。即ち、粗ＶＣタンク（２）に回
収された未反応塩化ビニルモノマー液には、水、エチル
クロライド、１，１−ジクロルエタン、１，２−ジクロ
ルエタン、Ｃ4炭化水素類等の高沸点不純物が含有され
ている。この高沸点不純物が含有されている状態で回収
された未反応塩化ビニルモノマー液をそのままの状態で
次回の塩化ビニルの重合に再利用して塩化ビニルの重合
を行うと、 （イ）重合時間が遅延する （ロ）重合終了後、重合器内壁面の重合体スケールの付
着が著しく増加する （ハ）重合終了後、得られる塩化ビニル重合体の熱安定
性が低下し、また、得られる塩化ビニル重合体製品のフ
ィシュアイが増加する等の製品の品質低下を招くなどの
不都合が生じるので好ましくなく、この蒸留精製工程
（３）においては、上記例示された高沸点不純物を除去
するものである。The recovered unreacted vinyl chloride monomer gas is liquefied through the liquefaction step (1) and stored in the crude VC tank (2). The recovered unreacted vinyl chloride monomer liquid stored in the crude VC tank (2) is distilled and purified (3).
To be purified. That is, the unreacted vinyl chloride monomer liquid recovered in the crude VC tank (2) contains high boiling impurities such as water, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, and C 4 hydrocarbons. Has been done. When the unreacted vinyl chloride monomer liquid recovered in the state of containing the high boiling impurities is reused as it is for the next polymerization of vinyl chloride to polymerize vinyl chloride, (a) the polymerization time is (B) After the completion of the polymerization, the adhesion of polymer scale on the inner wall surface of the polymerization vessel remarkably increases. (C) After the completion of the polymerization, the thermal stability of the obtained vinyl chloride polymer decreases, and the obtained vinyl chloride This is not preferable because it causes inconveniences such as increase in fisheye of the polymer product and deterioration of product quality. In this distillation purification step (3), the high boiling point impurities exemplified above are removed.
【０００５】蒸留精製工程（３）を通された回収未反応
塩化ビニルモノマー液は、回収ＶＣタンク（４）に貯蔵
される。このように回収ＶＣタンク（４）に貯蔵された
回収未反応塩化ビニルモノマー液は、次回の塩化ビニル
の重合時に重合器（５）内へ供給されて再利用される。The recovered unreacted vinyl chloride monomer liquid that has passed through the distillation purification step (3) is stored in the recovered VC tank (4). The recovered unreacted vinyl chloride monomer liquid stored in the recovered VC tank (4) in this way is supplied into the polymerization vessel (5) and reused during the next polymerization of vinyl chloride.
【０００６】回収未反応塩化ビニルモノマーガスは、以
上説明したように塩化ビニルの重合に再利用されている
が、従来、図１の液化工程（１）後の工程における粗Ｖ
Ｃタンク（２）内の壁面や液化工程（１）から蒸留精製
工程（３）までに通ずる配管内の壁面、特に粗ＶＣタン
ク（２）内壁面への塩化ビニルモノマーの重合反応物の
生成付着が著しいという問題があった。Although the recovered unreacted vinyl chloride monomer gas is reused for the polymerization of vinyl chloride as described above, conventionally, the crude V in the step after the liquefaction step (1) in FIG. 1 is used.
Formation and adhesion of vinyl chloride monomer polymerization reaction product to the wall surface in the C tank (2) and the wall surface in the pipe that leads from the liquefaction step (1) to the distillation and purification step (3), particularly the inner wall surface of the crude VC tank (2). There was a problem that it was remarkable.
【０００７】また、図１で蒸留精製された回収未反応塩
化ビニルモノマー液は、回収ＶＣタンク（４）内で貯蔵
されるが、貯蔵されている間に回収ＶＣタンク（４）内
の壁面に塩化ビニルモノマーの重合反応物が生成付着す
る問題もあった。The recovered unreacted vinyl chloride monomer liquid distilled and purified in FIG. 1 is stored in the recovery VC tank (4). There is also a problem that a polymerization reaction product of a vinyl chloride monomer is generated and attached.
【０００８】従って、上記のように回収塩化ビニルモノ
マー液を貯蔵する場合、粗ＶＣタンク（２）内壁面、液
化工程（１）から蒸留精製工程（３）までに通ずる配管
内壁面、回収ＶＣタンク（４）内壁面に重合体スケール
が付着するので定期的に付着した重合体スケールの除去
作業を行う必要があり、生産性低下の原因となってい
た。Therefore, when storing the recovered vinyl chloride monomer liquid as described above, the inner wall surface of the crude VC tank (2), the inner wall surface of the pipe leading from the liquefaction step (1) to the distillation purification step (3), and the recovered VC tank (4) Since the polymer scale adheres to the inner wall surface, it is necessary to periodically remove the adhered polymer scale, which causes a decrease in productivity.
【０００９】この対策として、回収未反応塩化ビニルモ
ノマーの重合反応物の生成を防ぐために、液化工程
（１）に入る前工程で重合禁止剤を添加する方法がとら
れているが、粗ＶＣタンク（２）の内壁面や、液化工程
（１）から蒸留精製工程（３）までに通ずる配管の内壁
面への重合体スケールの付着を十分に防止できず、満足
できるものではなかった。As a countermeasure against this, a method of adding a polymerization inhibitor in the step before the liquefaction step (1) is taken in order to prevent the formation of the polymerization reaction product of the recovered unreacted vinyl chloride monomer. The polymer scale could not be sufficiently prevented from adhering to the inner wall surface of (2) or the inner wall surface of the pipe leading from the liquefaction step (1) to the distillation purification step (3), which was not satisfactory.
【００１０】一方、回収ＶＣタンク（４）内壁面への重
合体スケール付着の問題の対策としても、上記と同様に
回収ＶＣタンク（４）内へ重合禁止剤を添加する方法が
考えられるが、回収ＶＣタンク（４）内壁面への重合体
スケール付着を防止するためには多量の重合禁止剤を添
加する必要がある。この場合、多量に重合禁止剤を含有
した塩化ビニルモノマー液を次回の塩化ビニルの重合時
に重合器（５）内へ供給して塩化ビニルの重合を行うこ
とになるが、その結果、 （イ）重合時間が遅延する等、重合条件に影響を与える （ロ）得られる塩化ビニル重合体の製品品質、嵩比重、
粒度分布、可塑剤吸収性等の品質物性に悪影響を与える ので好ましくない。結果的には、重合禁止剤の添加は制
限されており、重合体スケールの付着を十分に防止する
ことができなかった。On the other hand, as a measure against the problem of polymer scale adhesion on the inner wall surface of the recovered VC tank (4), a method of adding a polymerization inhibitor into the recovered VC tank (4) is conceivable as in the above. In order to prevent the polymer scale from adhering to the inner wall surface of the recovery VC tank (4), it is necessary to add a large amount of polymerization inhibitor. In this case, the vinyl chloride monomer liquid containing a large amount of the polymerization inhibitor is fed into the polymerization vessel (5) at the time of the next polymerization of vinyl chloride to perform the polymerization of vinyl chloride. As a result, (a) Affects polymerization conditions such as delaying polymerization time. (B) Product quality, bulk specific gravity, and product quality of the resulting vinyl chloride polymer.
This is not preferable because it adversely affects the quality physical properties such as particle size distribution and plasticizer absorbability. As a result, the addition of the polymerization inhibitor was limited, and the adhesion of the polymer scale could not be sufficiently prevented.
【００１１】また、回収ＶＣタンク（４）内壁面への重
合体スケールの付着の問題の対策として、蒸留精製工程
（３）で除去しきれない、エチレン、エタン、アセチレ
ン、ｎ−ブタン、プロピレン、メチルクロライド等の低
沸点不純物が含有されているので、更にこれらを含有し
ている低沸点不純物を除去する精製工程設備を設けるこ
とも考えられるが、これら低沸点不純物を除去する精製
工程設備は複雑であり、この設備を設けると費用がかか
り、かえってコスト高となり、経済的に不利で好ましく
ない。Further, as a measure against the problem of adhesion of polymer scale to the inner wall surface of the recovery VC tank (4), ethylene, ethane, acetylene, n-butane, propylene, which cannot be completely removed in the distillation and purification step (3), Since low-boiling point impurities such as methyl chloride are contained, it may be possible to further install refining step equipment for removing low-boiling point impurities containing these, but the refining step equipment for removing these low-boiling point impurities is complicated. However, the provision of this equipment is costly and rather expensive, which is economically disadvantageous and not preferable.
【００１２】本発明は上記事情を改善するためになされ
たもので、上記粗ＶＣタンクの内壁面、液化工程から蒸
留精製工程に至る配管の内壁面、回収ＶＣタンクの内壁
面に対する重合体スケールの付着を可及的に防止するこ
とができる回収未反応塩化ビニルモノマーの貯蔵方法を
提供することを目的とする。The present invention has been made in order to improve the above-mentioned circumstances, and a polymer scale for the inner wall surface of the crude VC tank, the inner wall surface of the pipe from the liquefaction process to the distillation / purification process, and the inner wall surface of the recovery VC tank. It is an object of the present invention to provide a storage method of recovered unreacted vinyl chloride monomer capable of preventing adhesion as much as possible.
【００１３】[0013]
【課題を解決するための手段及び発明の実施の形態】本
発明者らは、上記目的を達成するため鋭意検討を行った
結果、回収未反応塩化ビニルモノマーに対し、塩化ビニ
ルの重合にはじめて供給されるべきフレッシュな塩化ビ
ニルモノマーを添加することが、重合体スケールの壁面
への付着に効果的であることを知見した。Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the recovered unreacted vinyl chloride monomer is supplied for the first time to the polymerization of vinyl chloride. It has been found that the addition of fresh vinyl chloride monomer to be done is effective in adhering to the wall of the polymer scale.
【００１４】即ち、上記液化工程で液化された液化回収
未反応塩化ビニルモノマーにフレッシュ塩化ビニルモノ
マーを添加した場合、上記粗ＶＣタンクの内壁面に対す
る重合体スケールの付着、更には液化工程から蒸留精製
工程に至る配管の内壁面に対する重合体スケールの付着
が防止されること、この場合、上記フレッシュ塩化ビニ
ルモノマーの添加と共に重合禁止剤を添加することによ
り、更に確実に重合体スケールの付着が防止されること
を見い出した。That is, when the fresh vinyl chloride monomer is added to the liquefied and recovered unreacted vinyl chloride monomer liquefied in the liquefaction step, the polymer scale is attached to the inner wall surface of the crude VC tank, and further the liquefaction step is followed by distillation purification. The adhesion of the polymer scale to the inner wall surface of the pipe leading to the process is prevented, and in this case, the addition of the polymerization inhibitor together with the addition of the fresh vinyl chloride monomer further reliably prevents the adhesion of the polymer scale. I found that.
【００１５】また、上記フレッシュ塩化ビニルモノマー
を液化され、精製された回収未反応塩化ビニルモノマー
に添加した場合、上記回収ＶＣタンクの内壁面に重合体
スケールが付着することを有効に防止し得ることを見い
出したものである。When the fresh vinyl chloride monomer is added to the recovered unreacted vinyl chloride monomer which has been liquefied and purified, it is possible to effectively prevent the polymer scale from adhering to the inner wall surface of the recovered VC tank. I found out.
【００１６】従って、本発明は、（１）回収未反応塩化
ビニルモノマーにフレッシュ塩化ビニルモノマーを添加
することを特徴とする回収未反応塩化ビニルモノマーの
貯蔵方法、（２）回収未反応塩化ビニルモノマーが、液
化工程で液化された液化回収未反応塩化ビニルモノマー
であり、更に該液化回収未反応塩化ビニルモノマーに重
合禁止剤を添加することを特徴とする上記の回収未反応
塩化ビニルモノマーの貯蔵方法、及び（３）回収未反応
塩化ビニルモノマーが、液化工程で液化され、次いで蒸
留精製工程で高沸点不純物が除去されたものであること
を特徴とする上記の回収未反応塩化ビニルモノマーの貯
蔵方法を提供する。Accordingly, the present invention provides (1) a method for storing recovered unreacted vinyl chloride monomer, characterized by adding fresh vinyl chloride monomer to recovered unreacted vinyl chloride monomer, and (2) recovered unreacted vinyl chloride monomer. Is a liquefied and recovered unreacted vinyl chloride monomer liquefied in the liquefaction step, and a polymerization inhibitor is added to the liquefied and recovered unreacted vinyl chloride monomer. And (3) the method for storing recovered unreacted vinyl chloride monomer, wherein the recovered unreacted vinyl chloride monomer is liquefied in a liquefaction step and then high boiling point impurities are removed in a distillation and purification step. I will provide a.
【００１７】以下、本発明につき更に詳しく説明する
と、本発明の回収未反応塩化ビニルモノマーの貯蔵方法
は、上述したように、回収未反応塩化ビニルモノマーに
フレッシュ塩化ビニルモノマーを添加するものである。
この場合、フレッシュ塩化ビニルモノマーの添加は、回
収未反応塩化ビニルモノマーガスの液化工程前、液化工
程時、液化工程後のいずれの時期に行ってもよく、重合
スケールの壁面への付着を防止すべき箇所によって適宜
選定されるが、特に液化工程時又は液化直後にフレッシ
ュ塩化ビニルモノマーが添加された状態にあり、これに
よって粗ＶＣタンク内壁面、液化工程から蒸留精製工程
に至る配管内壁面、更には回収ＶＣタンク内壁面に重合
体スケールが付着することを防止することが好適であ
る。なおこの場合、フレッシュ塩化ビニルモノマーに加
えて重合禁止剤を添加することが推奨される。また、回
収ＶＣタンク内壁面に対する重合体スケールの付着防止
のためには、液化され、次いで精製された回収未反応塩
化ビニルモノマーにフレッシュ塩化ビニルモノマーを添
加することが有効である。この場合、この液化、精製回
収未反応塩化ビニルモノマーは、上記の液化工程時又は
液化直後に既にフレッシュ塩化ビニルモノマーが添加さ
れたものであっても、未だ添加されていないものであっ
てもよい。The present invention will be described in more detail below. In the method for storing recovered unreacted vinyl chloride monomer of the present invention, fresh vinyl chloride monomer is added to the recovered unreacted vinyl chloride monomer as described above.
In this case, the addition of the fresh vinyl chloride monomer may be performed at any time before the liquefaction step of the recovered unreacted vinyl chloride monomer gas, during the liquefaction step, and after the liquefaction step, and prevents the adhesion of the polymerization scale to the wall surface. Although it is appropriately selected depending on the place to be used, fresh vinyl chloride monomer is added especially during or immediately after the liquefaction process, whereby the inner wall surface of the crude VC tank, the inner wall surface of the pipe from the liquefaction process to the distillation purification process, and It is preferable to prevent the polymer scale from adhering to the inner wall surface of the recovery VC tank. In this case, it is recommended to add a polymerization inhibitor in addition to the fresh vinyl chloride monomer. Further, in order to prevent the polymer scale from adhering to the inner wall surface of the recovered VC tank, it is effective to add fresh vinyl chloride monomer to the recovered unreacted vinyl chloride monomer which has been liquefied and then purified. In this case, the liquefied, purified and recovered unreacted vinyl chloride monomer may be one to which the fresh vinyl chloride monomer has been added at the time of the above-mentioned liquefaction step or immediately after the liquefaction, or one not yet added. .
【００１８】上記の点を図１を参照して詳細に説明する
と、重合反応終了後、重合器内、スラリータンク内等か
ら未反応塩化ビニルモノマーガス回収配管を通じて未反
応塩化ビニルモノマーガスを回収する。上記回収された
回収未反応塩化ビニルモノマーガスはポンプ等により液
化工程（１）へ送られる。液化工程（１）に送られてき
た回収未反応塩化ビニルモノマーガスは、コンプレッサ
ーにより圧縮ガスにされ、次いで回収未反応塩化ビニル
モノマー圧縮ガスはコンデンサーにより液化される。液
化された回収未反応塩化ビニルモノマー液は粗ＶＣタン
ク（２）へ送られて粗ＶＣタンク（２）で貯蔵される。The above points will be described in detail with reference to FIG. 1. After the completion of the polymerization reaction, the unreacted vinyl chloride monomer gas is recovered from the unreacted vinyl chloride monomer gas recovery pipe from the inside of the polymerization vessel, the slurry tank or the like. . The recovered unreacted vinyl chloride monomer gas thus recovered is sent to the liquefaction step (1) by a pump or the like. The recovered unreacted vinyl chloride monomer gas sent to the liquefaction step (1) is made into a compressed gas by a compressor, and then the recovered unreacted vinyl chloride monomer compressed gas is liquefied by a condenser. The liquefied recovered unreacted vinyl chloride monomer liquid is sent to the crude VC tank (2) and stored in the crude VC tank (2).
【００１９】液化回収未反応塩化ビニルモノマー液は、
上記のように一度粗ＶＣタンク（２）で貯蔵されるが、
液化工程（１）後、粗ＶＣタンク（２）内で液化回収未
反応塩化ビニルモノマー液が貯蔵されている間、重合禁
止剤及びフレッシュ塩化ビニルモノマー液が液化回収未
反応塩化ビニルモノマー液に添加される。この場合、重
合禁止剤及びフレッシュ塩化ビニルモノマー液は、液化
工程（１）終了後、液化回収未反応塩化ビニルモノマー
液が粗ＶＣタンク（２）へ送られる配管に重合禁止剤又
はフレッシュ塩化ビニルモノマー液を添加する配管を接
続して添加してもよい。また、粗ＶＣタンク（２）に直
接添加してもよい。The liquefied and recovered unreacted vinyl chloride monomer liquid is
As described above, once stored in the crude VC tank (2),
After the liquefaction step (1), the polymerization inhibitor and the fresh vinyl chloride monomer solution are added to the liquefaction recovered unreacted vinyl chloride monomer solution while the liquefaction recovered unreacted vinyl chloride monomer solution is stored in the crude VC tank (2). To be done. In this case, after the liquefaction step (1), the polymerization inhibitor and the fresh vinyl chloride monomer liquid are used as a polymerization inhibitor or fresh vinyl chloride monomer in the pipe through which the liquefied and recovered unreacted vinyl chloride monomer liquid is sent to the crude VC tank (2). You may connect and add the pipe which adds a liquid. Alternatively, it may be added directly to the crude VC tank (2).
【００２０】重合禁止剤としては、ｐ−メトキシフェノ
ール、ｔ−ブチルヒドロキシアニソール（ＢＨＡ）、ｎ
−オクタデシル−３−（４’−ヒドロキシ−３’，５−
ジ−ブチルフェニル）プロピオネート、３，５−ジ−ｔ
−ブチル−４−ヒドロキシトルエン（ＢＨＴ）、トリエ
チレングリコール−ビス［３−（３−ｔ−ブチル−５−
メチル−４−ヒドロキシフェニル）プロピオネート］、
１，６−ヘキサンジオール−ビス［３−（３，５−ジ−
ｔ−ブチル−４−ヒドロキシフェニル）プロピオネー
ト］、２，２−チオ−ジエチレンビス［３−（３，５−
ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネ
ート］、２，２−チオビス（４−メチル−６−ブチルフ
ェノール）、２−ｔ−ブチル−４−ヒドロキシ−アニソ
ール、２，２’−メチレンビス（４−メチル−６−ｔ−
ブチルフェノール）、４，４’−ブチリデンビス（３−
メチル−６−ｔ−ブチルフェノール）、１，１，３−ト
リス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフ
ェニル）ブタン、２，５−ジ−ｔ−ブチルハイドロキノ
ン、２，２−ビス（４’−オキシフェニル）プロパン等
のフェノール系重合禁止剤；２，４−ビス（ｎ−オクチ
ルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブ
チルアニリノ）−１，３，５−トリアジン、Ｎ−フェニ
ル−Ｎ’−イソプロピル−ｐ−フェニレンジアミン、Ｎ
−フェニル−Ｎ’−（１，３−ジメチルブチル）−ｐ−
フェニレンジアミン、Ｎ，Ｎ’−ジフェニル−ｐ−フェ
ニレンジアミン、２，２，４−トリメチル−１，２−ジ
ヒドロキノリン重合物、ジアリル−ｐ−フェニレンジア
ミン等のアミン系重合禁止剤；ジラウリル・チオジプロ
ピオネート、ジスチアリル・チオジプロピオネート、２
−メルカプトベンゾイミダゾール等の硫黄系重合禁止
剤；ジステアリルペンタエリスリトールジホスファイト
等のリン系重合禁止剤などが挙げられるが、これらに限
定されるものではない。これらの酸化防止剤は単独又は
二種類以上組み合わせて使用される。As the polymerization inhibitor, p-methoxyphenol, t-butylhydroxyanisole (BHA), n
-Octadecyl-3- (4'-hydroxy-3 ', 5-
Di-butylphenyl) propionate, 3,5-di-t
-Butyl-4-hydroxytoluene (BHT), triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6-butylphenol), 2-t-butyl-4-hydroxy-anisole, 2,2'-methylenebis (4- Methyl-6-t-
Butylphenol), 4,4'-butylidenebis (3-
Methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2,5-di-t-butylhydroquinone, 2,2-bis Phenolic polymerization inhibitors such as (4′-oxyphenyl) propane; 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5 -Triazine, N-phenyl-N'-isopropyl-p-phenylenediamine, N
-Phenyl-N '-(1,3-dimethylbutyl) -p-
Amine-based polymerization inhibitors such as phenylenediamine, N, N'-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, diallyl-p-phenylenediamine; dilauryl thiodipro Pionate, distyaryl thiodipropionate, 2
-Sulfur-based polymerization inhibitors such as mercaptobenzimidazole; phosphorus-based polymerization inhibitors such as distearylpentaerythritol diphosphite, but not limited to these. These antioxidants are used alone or in combination of two or more.
【００２１】この重合禁止剤の添加量は、通常、液化回
収未反応塩化ビニルモノマー液１００重量部に対して、
０．０００２〜０．００５重量部、好ましくは０．００
０２〜０．００２重量部の割合がよい。この添加量が
０．０００２重量部未満であると重合体スケールの付着
防止効果を十分に得ることができない場合が生じ、ま
た、０．００５重量部を超えると液化回収未反応塩化ビ
ニルモノマーを重合器（５）内へ仕込んで再利用した場
合、重合時間が遅延するおそれがある。また、得られる
塩化ビニル重合体製品の初期着色性が悪化するばかり
か、それ以上の重合体スケールの付着防止効果を得るこ
とができず、経済的に不利である。The amount of the polymerization inhibitor added is usually 100 parts by weight of the liquefied and recovered unreacted vinyl chloride monomer liquid.
0.0002 to 0.005 parts by weight, preferably 0.00
The proportion of 02 to 0.002 parts by weight is preferable. If this addition amount is less than 0.0002 parts by weight, the effect of preventing adhesion of polymer scale may not be sufficiently obtained, and if it exceeds 0.005 parts by weight, liquefaction recovery unreacted vinyl chloride monomer is polymerized. When it is charged into the vessel (5) and reused, the polymerization time may be delayed. Further, not only the initial coloring property of the obtained vinyl chloride polymer product is deteriorated, but also the effect of preventing further adhesion of the polymer scale cannot be obtained, which is economically disadvantageous.
【００２２】この重合禁止剤の添加方法は、メタノー
ル、エタノール、トルエン等の有機溶剤に重合禁止剤を
溶解させて添加してもよく、またステアリン酸等の脂肪
酸、パラフィンスルホン酸、グリセリン−モノステアレ
ート等の多価アルコールの脂肪酸、ポリプロピレンオキ
サイド−ポリエチレンオキサイド−縮合生成物などの乳
化剤や、部分けん化ポリビニルアルコール、セルロース
誘導体などの懸濁剤及び水からなる水溶液に重合禁止剤
をホモジナイザー等により均一に分散させた分散液の状
態にして添加してもよい。As a method of adding the polymerization inhibitor, the polymerization inhibitor may be dissolved in an organic solvent such as methanol, ethanol or toluene, and added. Alternatively, a fatty acid such as stearic acid, paraffin sulfonic acid or glycerin-monostea can be added. A polyhydric alcohol fatty acid such as rate, an emulsifier such as polypropylene oxide-polyethylene oxide-condensation product, a partially saponified polyvinyl alcohol, a suspending agent such as a cellulose derivative, and a polymerization inhibitor are uniformly added to an aqueous solution of water by a homogenizer or the like. It may be added in the form of a dispersed dispersion.
【００２３】本発明の一態様においては、フレッシュ塩
化ビニルモノマーが、液化工程（１）以後、液化回収未
反応塩化ビニルモノマーに添加されるものであるが、こ
の液化回収未反応塩化ビニルモノマーには、通常重量割
合で不純物が１，０００ｐｐｍ以上含有されている。こ
の場合、フレッシュ塩化ビニルモノマー液が上述した液
化回収未反応塩化ビニルモノマー液へ添加されるもので
あるが、このフレッシュ塩化ビニルモノマー液は、塩化
ビニルの重合にはじめて供給される塩化ビニルモノマー
であり、このフレッシュ塩化ビニルモノマーに含有され
ている不純物は通常重量割合で５０ｐｐｍ以下である。
フレッシュ塩化ビニルモノマーの液化回収未反応塩化ビ
ニルモノマー液に対する添加量は、液化回収未反応塩化
ビニルモノマー液に対して液化フレッシュ塩化ビニルモ
ノマーを１容量％以上であり、好ましくは５〜３０容量
％添加される。添加量が１容量％未満であると、十分な
重合体スケール付着防止効果を得ることができない場合
がある。In one embodiment of the present invention, the fresh vinyl chloride monomer is added to the liquefied and recovered unreacted vinyl chloride monomer after the liquefaction step (1). In general, impurities are contained in an amount of 1,000 ppm or more in a weight ratio. In this case, the fresh vinyl chloride monomer solution is added to the above-mentioned liquefaction-recovered unreacted vinyl chloride monomer solution, but this fresh vinyl chloride monomer solution is the vinyl chloride monomer supplied for the first time in the polymerization of vinyl chloride. The impurities contained in the fresh vinyl chloride monomer are usually 50 ppm or less in weight ratio.
The amount of the fresh vinyl chloride monomer added to the liquefied and recovered unreacted vinyl chloride monomer liquid is 1% by volume or more, preferably 5 to 30% by volume, of the liquefied and recovered unreacted vinyl chloride monomer liquid. To be done. If the added amount is less than 1% by volume, a sufficient polymer scale adhesion preventing effect may not be obtained.
【００２４】次に、粗ＶＣタンク（２）に貯蔵された液
化回収未反応塩化ビニルモノマーは、蒸留精製工程
（３）に送られて精製される。この蒸留精製工程（３）
では回収未反応塩化ビニルモノマー液に含有される高沸
点不純物だけを除去するものであり、通常３０〜５０℃
の範囲で回収未反応塩化ビニルモノマー液を蒸留精製す
る。従ってこの蒸留精製工程の蒸留精製温度にもよる
が、通常、沸点が５５℃以上の１，２−ジクロルエチレ
ン（沸点６０．３℃）、１，１−ジクロルエタン（沸点
５７．３℃）、１，２−ジクロルエタン（沸点８３．５
℃）等の高沸点不純物は、ほぼ完全に除去されるが、沸
点が４１℃以下のエチルクロライド（沸点１２．３
℃）、メチレンクロライド（沸点４０．４℃）、メチル
クロライド（沸点−２３．７℃）等の低沸点不純物は除
去されない状態で回収未反応塩化ビニルモノマー液に含
有される。Next, the liquefied and recovered unreacted vinyl chloride monomer stored in the crude VC tank (2) is sent to the distillation purification step (3) for purification. This distillation purification step (3)
Is to remove only the high-boiling-point impurities contained in the recovered unreacted vinyl chloride monomer liquid, usually 30 to 50 ° C.
The recovered unreacted vinyl chloride monomer solution is distilled and purified in the range of. Therefore, depending on the distillation and purification temperature of this distillation and purification step, usually 1,2-dichloroethylene (boiling point 60.3 ° C) having a boiling point of 55 ° C or higher, 1,1-dichloroethane (boiling point 57.3 ° C), 1,2-dichloroethane (boiling point 83.5
High boiling impurities such as (° C.) Are almost completely removed, but ethyl chloride (boiling point 12.3 ° C) having a boiling point of 41 ° C or lower.
C.), methylene chloride (boiling point 40.4.degree. C.), methyl chloride (boiling point-23.7.degree. C.) and the like are contained in the recovered unreacted vinyl chloride monomer liquid without being removed.
【００２５】この蒸留精製工程で蒸留精製された回収未
反応塩化ビニルモノマー液には、上述したように低沸点
不純物を主とした不純物が重量割合で１，０００ｐｐｍ
以上含有されている。この蒸留精製された回収未反応塩
化ビニルモノマー液は回収ＶＣタンク（４）へ送られて
該タンク（４）内で貯蔵される。The recovered unreacted vinyl chloride monomer liquid distilled and purified in this distillation and purification process contains 1,000 ppm by weight of impurities mainly including low boiling point impurities as described above.
It is contained above. The recovered unreacted vinyl chloride monomer solution that has been purified by distillation is sent to the recovery VC tank (4) and stored in the tank (4).
【００２６】本発明の別の態様では、この蒸留精製工程
（３）を経た回収未反応塩化ビニルモノマー液が回収Ｖ
Ｃタンク（４）へ送られてきた時、回収ＶＣタンク
（４）内へフレッシュ塩化ビニルモノマー液が添加され
る。このフレッシュ塩化ビニルモノマー液は、塩化ビニ
ルの重合にはじめて供給される塩化ビニルモノマーであ
り、このフレッシュ塩化ビニルモノマーに含有されてい
る不純物は通常重量割合で５０ｐｐｍ以下である。フレ
ッシュ塩化ビニルモノマーの液化回収未反応塩化ビニル
モノマー液に対する添加量は、液化回収未反応塩化ビニ
ルモノマー液に対して液化フレッシュ塩化ビニルモノマ
ー１容量％以上であり、好ましくは５〜３０容量％添加
される。添加量が１容量％未満であると十分な重合体ス
ケール付着防止効果を得ることができず、好ましくな
い。In another aspect of the present invention, the recovered unreacted vinyl chloride monomer liquid obtained through the distillation and purification step (3) is recovered V
When sent to the C tank (4), the fresh vinyl chloride monomer liquid is added to the recovered VC tank (4). This fresh vinyl chloride monomer liquid is a vinyl chloride monomer supplied for the first time in the polymerization of vinyl chloride, and the impurities contained in this fresh vinyl chloride monomer are usually 50 ppm or less in weight ratio. The amount of the fresh vinyl chloride monomer added to the liquefied recovered unreacted vinyl chloride monomer liquid is 1 volume% or more of the liquefied fresh vinyl chloride monomer based on the liquefied recovered unreacted vinyl chloride monomer solution, and preferably 5 to 30 volume% is added. It If the addition amount is less than 1% by volume, a sufficient polymer scale adhesion preventing effect cannot be obtained, which is not preferable.
【００２７】また、フレッシュ塩化ビニルモノマーを添
加する場所については、回収ＶＣタンク（４）内に直接
添加してもよく、また蒸留精製工程（３）の終了後、回
収未反応塩化ビニルモノマー液が回収ＶＣタンク（４）
へ送られる配管にフレッシュ塩化ビニルモノマーを添加
する配管を接続してフレッシュ塩化ビニルモノマーを添
加してもよい。Regarding the place where the fresh vinyl chloride monomer is added, it may be added directly into the recovery VC tank (4), or the recovered unreacted vinyl chloride monomer liquid may remain after the distillation and purification step (3). Collection VC tank (4)
The fresh vinyl chloride monomer may be added by connecting a pipe for adding the fresh vinyl chloride monomer to the pipe sent to.
【００２８】なお、ここでフレッシュ塩化ビニルモノマ
ーが添加される液化、精製回収塩化ビニルモノマーは、
上述したように、その前工程でフレッシュ塩化ビニルモ
ノマーが添加されたものであっても、未添加のものであ
ってもよい。更に、この工程で上記した場合と同様にし
て重合禁止剤を添加することは有効である。The liquefied, purified and recovered vinyl chloride monomer to which the fresh vinyl chloride monomer is added is
As described above, the fresh vinyl chloride monomer may or may not be added in the previous step. Furthermore, it is effective to add a polymerization inhibitor in this step in the same manner as described above.
【００２９】また、この液化、精製回収塩化ビニルモノ
マーへのフレッシュ塩化ビニルモノマーの添加は、上記
した精製前の液化回収塩化ビニルモノマーにフレッシュ
塩化ビニルモノマーを添加した場合は必須ではなく、本
発明は少なくとも上記工程のいずれかの段階でフレッシ
ュ塩化ビニルモノマーが添加されればよい。The addition of fresh vinyl chloride monomer to the liquefied and purified vinyl chloride monomer is not essential when the fresh vinyl chloride monomer is added to the liquefied and recovered vinyl chloride monomer before purification as described above. It is sufficient that the fresh vinyl chloride monomer is added at least at any stage of the above steps.
【００３０】以上のようにフレッシュ塩化ビニルモノマ
ーが添加され、回収ＶＣタンクに貯蔵された回収未反応
塩化ビニルモノマーは、重合工程に送られ、再度塩化ビ
ニルの重合に供される。As described above, the fresh unreacted vinyl chloride monomer added with the fresh vinyl chloride monomer and stored in the recovered VC tank is sent to the polymerization step and is again subjected to the polymerization of vinyl chloride.
【００３１】[0031]
【実施例】以下、実施例及び比較例を示し、本発明を具
体的に説明するが、本発明は下記の実施例に制限される
ものではない。EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００３２】〔比較例１〕図１で示される粗ＶＣタンク
（２）として、内容積が１０ｍ3である鋼製粗ＶＣタン
ク（２）を使用した。Comparative Example 1 As the crude VC tank (2) shown in FIG. 1, a steel crude VC tank (2) having an internal volume of 10 m 3 was used.
【００３３】液化工程（１）よりこの粗ＶＣタンク
（２）へ送られてくる液化回収未反応塩化ビニルモノマ
ー液量に対して、約相等量の粗ＶＣタンク（２）内に貯
蔵されている液化回収未反応塩化ビニルモノマー液量を
次工程の蒸留精製工程（３）へ送り、常時粗ＶＣタンク
（２）内に３〜５ｍ3の塩化ビニルモノマー液を貯蔵す
るように６ケ月間連続使用した。The crude VC tank (2) is stored in the crude VC tank (2) in approximately the same amount as the liquid amount of the liquefied and recovered unreacted vinyl chloride monomer sent to the crude VC tank (2) from the liquefaction step (1). Liquefaction recovery Unreacted vinyl chloride monomer liquid amount is sent to the next step, distillation purification process (3), and continuously used for 6 months so that 3 to 5 m 3 of vinyl chloride monomer liquid is always stored in the crude VC tank (2). did.
【００３４】上記６ケ月間、液化回収未反応塩化ビニル
モノマーが粗ＶＣタンク（２）内へ供給される毎に、供
給された液化回収未反応塩化ビニルモノマー１００重量
部に対して重合禁止剤ｔ−ブチルヒドロキシアニソール
を０．００１重量部の割合で２０重量％トルエン溶液に
して粗ＶＣタンク（２）に添加した。Every time the liquefied and recovered unreacted vinyl chloride monomer is supplied into the crude VC tank (2) for the above 6 months, the polymerization inhibitor t is added to 100 parts by weight of the supplied liquefied and recovered unreacted vinyl chloride monomer. -Butylhydroxyanisole was added to the crude VC tank (2) as a 20 wt% toluene solution in a proportion of 0.001 part by weight.
【００３５】６か月後、粗ＶＣタンク（２）内及び粗Ｖ
Ｃタンク（２）から蒸留精製工程（３）へ通ずる配管内
にある液化回収未反応塩化ビニルモノマーを粗ＶＣタン
ク（２）、及び粗ＶＣタンク（２）から蒸留精製工程
（３）へ通ずる配管内より抜き出して粗ＶＣタンク
（２）内、及び粗ＶＣタンク（２）から蒸留精製工程
（３）へ通ずる配管内の重合体スケールの付着状況を観
察した。After 6 months, in the rough VC tank (2) and the rough V tank
Liquefied and recovered unreacted vinyl chloride monomer in the pipe leading from the C tank (2) to the distillation purification process (3) and the pipe leading from the crude VC tank (2) to the distillation purification process (3). The state of adhesion of the polymer scale was observed in the crude VC tank (2) and from the crude VC tank (2) and the pipe leading from the crude VC tank (2) to the distillation purification step (3).
【００３６】観察結果は下記の通りである。粗ＶＣタンク（２）内壁面 回収塩化ビニルモノマーの液が常時接触していた粗ＶＣ
タンク（２）内、液層部分の内壁面には塩化ビニルモノ
マーの重合反応生成物が全面にわたり２〜５ｍｍの厚さ
で付着していた。粗ＶＣタンク（２）より蒸留精製工程（３）へ通ずる配
管内 部分的に塩化ビニルモノマーの重合反応生成物が付着し
ており、その中には、配管がほとんど閉塞しそうなとこ
ろもあった。The observation results are as follows. Coarse VC tank (2) Recovered inner wall surface Coarse VC with vinyl chloride monomer liquid in constant contact
In the tank (2), a polymerization reaction product of a vinyl chloride monomer was attached to the inner wall surface of the liquid layer portion in a thickness of 2 to 5 mm over the entire surface. Distribution from crude VC tank (2) to distillation purification step (3)
A vinyl chloride monomer polymerization reaction product was partially adhered to the inside of the pipe, and in some of the places, the pipe was almost likely to be clogged.
【００３７】〔実施例１〕比較例１で使用した粗ＶＣタ
ンク（２）を使用し、液化工程（１）より液化回収未反
応塩化ビニルモノマー液が粗ＶＣタンク（２）内へ供給
されるごとに、（イ）供給された液化回収未反応塩化ビ
ニルモノマー液１ｍ3に対してフレッシュ塩化ビニルモ
ノマー液（不純物含有量３０ｐｐｍ）を０．１ｍ3の割
合で粗ＶＣタンク（２）内へ添加し、かつ、（ロ）供給
された液化回収未反応塩化ビニルモノマー液１００重量
部に対して重合禁止剤ｔ−ブチルヒドロキシアニソール
を０．００１重量部の割合で２０重量％トルエン溶液に
して粗ＶＣタンク（２）内へ添加した。Example 1 Using the crude VC tank (2) used in Comparative Example 1, the liquefaction-recovered unreacted vinyl chloride monomer liquid is supplied into the crude VC tank (2) from the liquefaction step (1). (A) Add fresh vinyl chloride monomer liquid (impurity content 30 ppm) to the crude VC tank (2) at a ratio of 0.1 m 3 to the supplied liquefaction recovery unreacted vinyl chloride monomer liquid 1 m 3 And (b) 0.001 part by weight of the polymerization inhibitor t-butylhydroxyanisole was added as a 20% by weight toluene solution to 100 parts by weight of the supplied liquefied and recovered unreacted vinyl chloride monomer liquid to prepare a crude VC. Added into tank (2).
【００３８】上記のように粗ＶＣタンク（２）内へ供給
される液化回収未反応塩化ビニルモノマー液及びフレッ
シュ塩化ビニルモノマー液の合計量に対して約相等量の
粗ＶＣタンク（２）内にある塩化ビニルモノマー液（液
化回収未反応塩化ビニルモノマー液とフレッシュ塩化ビ
ニルモノマー液の混合物）を次工程の蒸留精製工程
（３）へ送り、常時粗ＶＣタンク（２）内に３〜５ｍ3
の塩化ビニルモノマー液を貯蔵するように６ケ月間連続
使用した。As described above, in the crude VC tank (2), which is approximately equivalent to the total amount of the liquefied and recovered unreacted vinyl chloride monomer liquid and the fresh vinyl chloride monomer liquid supplied to the crude VC tank (2). A certain vinyl chloride monomer solution (a mixture of unreacted vinyl chloride monomer solution that has been liquefied and recovered and a fresh vinyl chloride monomer solution) is sent to the distillation purification step (3) of the next step, and 3-5 m 3 is constantly put in the crude VC tank (2).
The vinyl chloride monomer solution was used continuously for 6 months.
【００３９】６か月後、粗ＶＣタンク（２）内及び粗Ｖ
Ｃタンク（２）から蒸留精製工程（３）へ通ずる配管内
にある液化回収未反応塩化ビニルモノマーを粗ＶＣタン
ク（２）、及び粗ＶＣタンク（２）から蒸留精製工程
（３）へ通ずる配管内より抜き出して粗ＶＣタンク
（２）内、及び粗ＶＣタンク（２）から蒸留精製工程
（３）へ通ずる配管内の重合体スケールの付着状況を観
察した。After 6 months, in the coarse VC tank (2) and the coarse V tank
Liquefied and recovered unreacted vinyl chloride monomer in the pipe leading from the C tank (2) to the distillation purification process (3) and the pipe leading from the crude VC tank (2) to the distillation purification process (3). The state of adhesion of the polymer scale was observed in the crude VC tank (2) and from the crude VC tank (2) and the pipe leading from the crude VC tank (2) to the distillation purification step (3).
【００４０】観察結果は下記の通りである。粗ＶＣタンク（２）内壁面 粗ＶＣタンク（２）内の内壁面への重合反応生成物の付
着はほとんどなかった。粗ＶＣタンク（２）より蒸留精製工程（３）へ通ずる配
管内 内壁面への重合反応生成物の付着はほとんどなかった。The observation results are as follows. Inner wall surface of the rough VC tank (2) Almost no adhesion of the polymerization reaction product to the inner wall surface of the rough VC tank (2). Distribution from crude VC tank (2) to distillation purification step (3)
There was almost no adhesion of the polymerization reaction product to the inner wall surface of the tube .
【００４１】〔比較例２〕図１に示されている回収ＶＣ
タンク（４）として、内容積が１５ｍ3である鋼製回収
ＶＣタンク（４）を使用した。Comparative Example 2 Collected VC shown in FIG.
As the tank (4), a steel recovery VC tank (4) having an internal volume of 15 m 3 was used.
【００４２】蒸留精製工程（３）よりこの回収ＶＣタン
ク（４）へ送られてくる回収未反応塩化ビニルモノマー
液量に対して約相等量の回収ＶＣタンク（４）内に貯蔵
されている回収塩化ビニルモノマー液を次工程の重合器
（５）内へ送り、常時回収ＶＣタンク（４）内に５〜１
０ｍ3の塩化ビニルモノマー液を貯蔵するように６ケ月
間連続使用した。The recovery stored in the recovery VC tank (4) is approximately equivalent to the recovered unreacted vinyl chloride monomer liquid amount sent to the recovery VC tank (4) from the distillation purification step (3). The vinyl chloride monomer liquid is sent into the polymerization vessel (5) of the next step, and the recovery VC tank (4) constantly stores 5-1.
It was continuously used for 6 months to store 0 m 3 of vinyl chloride monomer solution.
【００４３】この間、回収ＶＣタンク（４）へ送られて
くる回収未反応塩化ビニルモノマーに含まれる不純物含
有量は５，０００ｐｐｍであった。During this period, the content of impurities contained in the recovered unreacted vinyl chloride monomer sent to the recovered VC tank (4) was 5,000 ppm.
【００４４】６か月後、回収ＶＣタンク（４）内にある
回収未反応塩化ビニルモノマーを回収ＶＣタンク（４）
より抜き出して、回収ＶＣタンク（４）内の重合体スケ
ールの付着状況を観察した。After 6 months, the recovered unreacted vinyl chloride monomer in the recovered VC tank (4) is recovered in the VC tank (4).
It was taken out further and the adhesion state of the polymer scale in the recovery VC tank (4) was observed.
【００４５】その結果、回収塩化ビニルモノマーの液が
常時接触していた回収ＶＣタンク（４）内液層部分の内
壁面には塩化ビニルモノマーの重合反応生成物が全面に
わたり約１０〜２０ｍｍの厚さで付着していた。As a result, the polymerization reaction product of the vinyl chloride monomer has a thickness of about 10 to 20 mm on the entire inner wall surface of the liquid layer portion of the recovery VC tank (4) which was constantly in contact with the liquid of the recovered vinyl chloride monomer. It was attached.
【００４６】〔実施例２〕比較例２で使用した回収ＶＣ
タンク（４）を使用し、蒸留精製工程（３）より回収未
反応塩化ビニルモノマー液（不純物含有量５，０００ｐ
ｐｍ）が回収ＶＣタンク（４）内へ供給されるごとに、
供給された回収未反応塩化ビニルモノマー液１ｍ3に対
してフレッシュ塩化ビニルモノマー液（不純物含有量３
０ｐｐｍ）を０．０５ｍ3の割合で回収ＶＣタンク
（４）内へ添加した。Example 2 Recovered VC used in Comparative Example 2
Unreacted vinyl chloride monomer liquid (impurity content of 5,000 p) recovered from the distillation purification step (3) using the tank (4)
pm) is supplied to the collection VC tank (4),
Fresh vinyl chloride monomer liquid to the supplied recovered unreacted vinyl chloride monomer liquid 1 m 3 (impurity content 3
0 ppm) was added to the recovery VC tank (4) at a rate of 0.05 m 3 .
【００４７】上記のように、回収ＶＣタンク（４）内へ
供給される回収未反応塩化ビニルモノマー液及びフレッ
シュ塩化ビニルモノマー液の合計量に対して約相等量の
回収ＶＣタンク（４）内にある塩化ビニルモノマー液
（回収未反応塩化ビニルモノマー液とフレッシュ塩化ビ
ニルモノマー液の混合物）を次工程の重合器（５）内へ
送り、常時回収ＶＣタンク（４）内に５〜１０ｍ3の塩
化ビニルモノマー液を貯蔵するように６ケ月間連続使用
した。As described above, in the recovery VC tank (4), an amount equivalent to the total amount of the recovered unreacted vinyl chloride monomer liquid and the fresh vinyl chloride monomer liquid supplied to the recovery VC tank (4) is obtained. A certain vinyl chloride monomer solution (a mixture of recovered unreacted vinyl chloride monomer solution and fresh vinyl chloride monomer solution) is sent into the polymerization vessel (5) of the next step, and 5-10 m 3 of chloride is constantly stored in the recovery VC tank (4). It was continuously used for 6 months to store the vinyl monomer solution.
【００４８】６か月後、回収ＶＣタンク（４）内にある
塩化ビニルモノマー液（回収未反応塩化ビニルモノマー
液とフレッシュ塩化ビニルモノマー液の混合物）を回収
ＶＣタンク（４）内より抜き出して回収ＶＣタンク
（４）内の重合体スケールの付着状況を観察した。After 6 months, the vinyl chloride monomer liquid (a mixture of the recovered unreacted vinyl chloride monomer liquid and the fresh vinyl chloride monomer liquid) in the recovery VC tank (4) is withdrawn from the recovery VC tank (4) and recovered. The state of adhesion of the polymer scale in the VC tank (4) was observed.
【００４９】その結果、回収ＶＣタンク（４）内の内壁
面への塩化ビニルモノマーの重合反応生成物の付着はほ
とんどなかった。As a result, the vinyl chloride monomer polymerization reaction product was hardly attached to the inner wall surface of the recovered VC tank (4).
【００５０】[0050]
【発明の効果】本発明によれば、重合スケールの各種タ
ンクや配管内壁面への付着を防止して回収未反応塩化ビ
ニルモノマーを貯蔵できる。According to the present invention, the recovered unreacted vinyl chloride monomer can be stored while preventing the polymerized scale from adhering to the inner wall surfaces of various tanks and pipes.
【図１】回収未反応塩化ビニルモノマーの処理工程を説
明するフローシートである。FIG. 1 is a flow sheet illustrating a treatment process of recovered unreacted vinyl chloride monomer.
１ 液化工程 ２ 粗ＶＣタンク ３ 蒸留精製工程 ４ 回収ＶＣタンク ５ 重合器 1 Liquefaction process 2 Crude VC tank 3 Distillation purification process 4 Recovery VC tank 5 Polymerizer
フロントページの続き (72)発明者 天野 正 茨城県鹿島郡神栖町大字東和田１番地 信 越化学工業株式会社塩ビ技術研究所内Front Page Continuation (72) Inventor Tadashi Amano No. 1 Towada, Kamisu Town, Kashima District, Ibaraki Prefecture Shin-Etsu Chemical Co., Ltd.
Claims (3)
シュ塩化ビニルモノマーを添加することを特徴とする回
収未反応塩化ビニルモノマーの貯蔵方法。1. A method of storing recovered unreacted vinyl chloride monomer, which comprises adding fresh vinyl chloride monomer to recovered unreacted vinyl chloride monomer.
工程で液化された液化回収未反応塩化ビニルモノマーで
あり、更に該液化回収未反応塩化ビニルモノマーに重合
禁止剤を添加することを特徴とする請求項１記載の回収
未反応塩化ビニルモノマーの貯蔵方法。2. The recovered unreacted vinyl chloride monomer is liquefied recovered unreacted vinyl chloride monomer liquefied in the liquefaction step, and a polymerization inhibitor is added to the liquefied recovered unreacted vinyl chloride monomer. The method for storing the recovered unreacted vinyl chloride monomer according to claim 1.
工程で液化され、次いで蒸留精製工程で高沸点不純物が
除去されたものであることを特徴とする請求項１記載の
回収未反応塩化ビニルモノマーの貯蔵方法。3. The recovered unreacted vinyl chloride monomer as claimed in claim 1, wherein the recovered unreacted vinyl chloride monomer is liquefied in the liquefaction step and then the high boiling point impurities are removed in the distillation purification step. Storage method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337898A JPH09157324A (en) | 1995-12-01 | 1995-12-01 | Method for storing recovered unreacted vinyl chloride monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337898A JPH09157324A (en) | 1995-12-01 | 1995-12-01 | Method for storing recovered unreacted vinyl chloride monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09157324A true JPH09157324A (en) | 1997-06-17 |
Family
ID=18313045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337898A Pending JPH09157324A (en) | 1995-12-01 | 1995-12-01 | Method for storing recovered unreacted vinyl chloride monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09157324A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039377A (en) * | 2005-08-03 | 2007-02-15 | Tokuyama Corp | Storage method of vinyl chloride monomer |
| KR20150025805A (en) * | 2013-08-30 | 2015-03-11 | 주식회사 엘지화학 | Apparatus for polymerizing vinyl chloride monomer and polymerization method of vinyl chloride monomer |
| KR20220021529A (en) | 2020-08-14 | 2022-02-22 | 주식회사 엘지화학 | Dividing wall distilation column |
| WO2023080545A1 (en) * | 2021-11-03 | 2023-05-11 | 한화솔루션 주식회사 | Method and apparatus for recovering unreacted monomer |
-
1995
- 1995-12-01 JP JP7337898A patent/JPH09157324A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039377A (en) * | 2005-08-03 | 2007-02-15 | Tokuyama Corp | Storage method of vinyl chloride monomer |
| KR20150025805A (en) * | 2013-08-30 | 2015-03-11 | 주식회사 엘지화학 | Apparatus for polymerizing vinyl chloride monomer and polymerization method of vinyl chloride monomer |
| KR20220021529A (en) | 2020-08-14 | 2022-02-22 | 주식회사 엘지화학 | Dividing wall distilation column |
| WO2023080545A1 (en) * | 2021-11-03 | 2023-05-11 | 한화솔루션 주식회사 | Method and apparatus for recovering unreacted monomer |
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