JP3545440B2 - Viscosity increase inhibitor for aromatic unsaturated compound and method thereof - Google Patents
Viscosity increase inhibitor for aromatic unsaturated compound and method thereof Download PDFInfo
- Publication number
- JP3545440B2 JP3545440B2 JP31669793A JP31669793A JP3545440B2 JP 3545440 B2 JP3545440 B2 JP 3545440B2 JP 31669793 A JP31669793 A JP 31669793A JP 31669793 A JP31669793 A JP 31669793A JP 3545440 B2 JP3545440 B2 JP 3545440B2
- Authority
- JP
- Japan
- Prior art keywords
- salt
- oil
- viscosity
- general formula
- aromatic unsaturated
- 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.)
- Expired - Lifetime
Links
- 239000003112 inhibitor Substances 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 title claims description 21
- 125000003118 aryl group Chemical group 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 238000010791 quenching Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 239000004480 active ingredient Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000001629 suppression Effects 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000003921 oil Substances 0.000 description 38
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 10
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 5
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical class CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- -1 tertiary amine salt Chemical class 0.000 description 5
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical class CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical class CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- PVXSFEGIHWMAOD-UHFFFAOYSA-N 2-tridecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O PVXSFEGIHWMAOD-UHFFFAOYSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- MCVUKOYZUCWLQQ-UHFFFAOYSA-N tridecylbenzene Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1 MCVUKOYZUCWLQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical class CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- AZLNHMGSTZDDIY-UHFFFAOYSA-N 1-nonylnaphthalene Chemical compound C1=CC=C2C(CCCCCCCCC)=CC=CC2=C1 AZLNHMGSTZDDIY-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-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
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SRQYCPBEEPGBTN-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid tetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O SRQYCPBEEPGBTN-UHFFFAOYSA-N 0.000 description 1
- HXDXZZNFARDZLT-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O HXDXZZNFARDZLT-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical class CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical class CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 1
- YMTCDSQBRGXFML-UHFFFAOYSA-N 2-tert-butylbenzenesulfonic acid Chemical compound CC(C)(C)C1=CC=CC=C1S(O)(=O)=O YMTCDSQBRGXFML-UHFFFAOYSA-N 0.000 description 1
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 description 1
- JOZZAIIGWFLONA-UHFFFAOYSA-N 3-methylbutan-2-amine Chemical class CC(C)C(C)N JOZZAIIGWFLONA-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- ZEZSYLKJRJYGEQ-UHFFFAOYSA-N 4-n-octan-2-ylbenzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(N)C=C1 ZEZSYLKJRJYGEQ-UHFFFAOYSA-N 0.000 description 1
- FCQAFXHLHBGGSK-UHFFFAOYSA-N 4-nonyl-n-(4-nonylphenyl)aniline Chemical compound C1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1 FCQAFXHLHBGGSK-UHFFFAOYSA-N 0.000 description 1
- MEPYMUOZRROULQ-UHFFFAOYSA-N 4-tert-butyl-2,6-dimethylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(C)=C1O MEPYMUOZRROULQ-UHFFFAOYSA-N 0.000 description 1
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical class CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- PBSPSRFLAPUKGI-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(O)=CC1)O.C(CCC)N Chemical compound C(C)(C)(C)C=1C=C(C(O)=CC1)O.C(CCC)N PBSPSRFLAPUKGI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical class CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical class CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical class CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical class CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZKXYINRKIDSREX-UHFFFAOYSA-N n,n-dipropylhydroxylamine Chemical compound CCCN(O)CCC ZKXYINRKIDSREX-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical class CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- 150000003941 n-butylamines Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical class CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical class CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- VXNSQGRKHCZUSU-UHFFFAOYSA-N octylbenzene Chemical compound [CH2]CCCCCCCC1=CC=CC=C1 VXNSQGRKHCZUSU-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical class CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical class CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical class CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical class CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、オレフィン製造プロセスにおけるオイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇を抑制することにより、製品収率の向上，熱効率向上、運転の安定化等を目的とした、前記芳香族不飽和化合物の粘度上昇抑制剤および粘度上昇抑制方法に関する。
【０００２】
【従来の技術】
石油化学工業におけるオレフィン類の製造は、通常、ナフサの熱分解によって行われる。ナフサは熱分解炉で希釈スチームと共に８００〜８５０℃で熱分解され、分解炉出口で３５０〜４００℃まで急冷された後、オイルクエンチ塔（ガソリンフラクショネーター、ガソリン精留塔ともいわれる）へ送られ、ここで炭素数９以下の軽質分と、それ以上の重質分とに分けられる。オイルクエンチ塔のフィード油中には、スチレン，メチルスチレン、 ジビニルベンゼン，インデン等の芳香族不飽和化合物が含まれており、これら化合物がオイルクエンチ塔内、あるいは塔底部で熱により重合して、塔底油の粘度が上昇、あるいは塔内での重合物による汚れ等の原因となる。従来、塔内での汚れを防止するために、重合禁止剤の添加が専ら行われていたが、これは単に重合抑制による汚れ防止であり、ある程度の効果が認められるものの、塔底油の粘度上昇を抑制するまでには至らない。従って、塔底油の粘度上昇を抑えるためには、塔底部温度を低く抑えてこれに対処するのが一般的であつた。
【０００３】
【発明が解決しようとする課題】
解決しようとする問題点は、オレフィン類製造プロセスにおいて、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇を抑制させることが可能な薬剤およびその方法を提供することである。
【０００４】
【課題を解決するための手段】
本発明者らは、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇は、フィード油中に含まれるスチレン，メチルスチレン、ジビニルベンゼン，インデン等の芳香族不飽和化合物の熱重合に起因するという推定から、重合抑制および粘度上昇機構について鋭意研究を行った結果、該塔底の芳香族不飽和化合物の粘度上昇に対する抑制可能な化合物を見いだし、本発明を完成するに至った。
【０００５】
すなわち、本発明は、下記一般式（I）で表されるスルフォン酸、あるいはその塩類（式中Ｒ1は炭素数４〜３２の直鎖、もしくは分岐構造を有するアルキル基；又はアルキル置換ベンゼン核あるいはアルキル置換ナフタレン核で、置換アルキル基のうち少なくとも１つは炭素数４〜３２の直鎖、もしくは分岐構造を有する。Ｘは水素、アルカリ金属、アルカリ土類金属、あるいは炭素数１〜２２の直鎖，もしくは分岐構造を有する一級、二級、もしくは三級アミン塩で、分子中にヒドロキシル基、あるいはアルコキシル基をもっていてもよい。ｎは１あるいは１/２である。）の一種以上を有効成分として含有することを特徴とする、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇抑制剤である。これにさらに芳香族アミン系重合禁止剤、フェノール系重合禁止剤、ジアルキルヒドロキシルアミン系重合禁止剤から選ばれた一種以上を，下記一般式（I）の化合物に、配合することよりなる前記芳香族不飽和化合物の粘度上昇抑制剤である。
【０００６】
Ｒ1−ＳＯ3［Ｘ］n ．．．（I）
また、ナフサ，軽油，天然ガス、液化天然ガス等の炭化水素類を原料として、これらを熱分解することによりオレフィン類を製造するプロセスでのオイルクエンチ塔において、塔底油量に対し、上記一般式（I）のスルフォン酸、あるいはその塩の有効成分を１０ｐｐｍ〜１万ｐｐｍに保つように、当該薬剤を塔底油に添加することによる、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇抑制方法を提供するものである。
【０００７】
本発明の有効成分は上記一般式（Ｉ）で表されるスルフォン酸、あるいはその塩類であり、Ｒ１は、ノニル、ドデシル、オクタデシル、石油スルホン酸残基、ドデシルベンゼン、トリ−デシルベンゼン、ジブチルベンゼン、オクチルべンゼン、ノニルベンゼン、ノニルナフタレンである。また、Ｘとしては、水素；リチウム、 ナトリウム、カリウム等のアルカリ金属、マグネシウム、バリウム、カルシウム等のアルカリ土類金属；プロピルアミン塩、ジプロピルアミン塩、ブチルアミン塩、ジブチルアミン塩、トリブチルアミン塩、イソブチルアミン塩、ジイソブチルアミン塩、ｓｅｃ−ブチルアミン塩、ジ−ｓｅｃ−ブチルアミン塩、１，２−ジメチルプロピルアミン塩、ヘキシルアミン塩、シクロヘキシルアミン塩、ヘプチルアミン塩、２−エチルヘキシルアミン塩、ジ−（２−エチルヘキシル）アミン塩、オクチルアミン塩、ノニルアミン塩、デシルアミン塩、ウンデシルアミン塩、ドデシルアミン塩、テトラデシルアミン塩、ヘキサデシルアミン塩、オクタデシルアミン塩、ヤシアルキルアミン塩、 モノエタノールアミン塩等のアルキルアミン塩が挙げられる。具体的な例としては、 ドデシルベンゼンスルフォン酸ナトリウム、 石油スルフォン酸ナトリウム、 ドデシルベンゼンスルフォン酸ヤシアルキルアミン塩、 ドデシルベンゼンスルフォン酸モノエタノールアミン塩等がある。これらスルフォン酸、あるいはその塩類は、 一種類単独で用いること、もしくは二種以上を組み合わせて用いることもあり、本発明はこれら混合使用になんら制限を加えるものではない。
【０００８】
また本発明の重合禁止剤は、一般にラジカル連鎖禁止作用に基づく酸化防止剤と同意義に定義されるもので、芳香族アミン系重合禁止剤としては、ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−ジイソプロピル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−ｓｅｃ−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、Ｎ−（１−メチルヘプチル）−ｐ−フェニレンジアミン等のｐ−フェニレンジアミン類；４，４´−ジクミル−ジフェニルアミン、４，４´−ジオクチル−ジフェニルアミン、ｐ−メトキシフェニルメチルアミン、４，４´−ジノニルジフェニルアミン、ジフェニルアミン、フェニル−α−ナフチルアミン、フェニル−β−ナフチルアミン等の二級アミン類が挙げられる。フェノール系重合禁止剤としては、フェノール、２−メチルフェノール、４−メチルフェノール、２，６−ジメチルフェノール、２，４，６−トリメチルフェノール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，４−ジ−ｔｅｒｔ−ブチルフェノール、２−メチル−４−ｔｅｒｔ−ブチルフェノール、２，６−ジイソプロピルフェノール、２，６−ジメチル−４−ｔｅｒｔ−ブチルフェノール、４−メトキシフェノール等のフェノール類；４−ｔｅｒｔ−ブチルカテコール等のカテコール類；ハイドロキノン、２−メチルハイドロキノン、２−ｔｅｒｔ−ブチルハイドロキノン、２，５−ジ−ｔｅｒｔ−ブチルハイドロキノン、２，５−ジ−ｔｅｒｔ−アミルハイドロキノン等のハイドロキノン類等が挙げられる。ジアルキルヒドロキシルアミン系重合禁止剤としては、 ジエチルヒドロキシルアミン、 ジプロピルヒドロキシルアミン等が挙げられる。
【０００９】
これら重合禁止剤は、１種類単独で用いること、もしくは２種以上を組み合わせて用いることもあり、本発明はこれら重合禁止剤の混合使用になんら制限を加えるものではない。
本発明の重合禁止剤をスルフォン酸あるいはその塩類に配合使用する場合、その配合比は、上記一般式（Ｉ）のスルフォン酸、あるいはその塩類に対し、１０（重量）倍以下である。
本発明の粘度上昇抑制剤の添加量は、オイルクエンチ塔塔底油量に対し、上記一般式（Ｉ）のスルフォン酸、あるいはその塩の有効成分を１０ｐｐｍ〜１万ｐｐｍ、好ましくは１０ｐｐｍ〜２０００ｐｐｍに保つようにする。１０ｐｐｍ未満では、充分な効果が期待出来ず、また１万ｐｐｍより多いと、効果としては充分あるが、添加量の割りには効果が上がらず、経済的にみて好ましくはない。
【００１０】
本発明の粘度上昇抑制剤の注入箇所は、特に限定されるものではないが、通常オイルクエンチ塔フィード油，還流油に添加、または直接オイルクエンチ塔塔底液に添加される。
また、本発明の粘度上昇抑制剤の添加にあたっては、各有効成分をそれぞれ別個に添加する、もしくは所定量の割合で混合しておき添加する。しかし、取り扱い易さなどから、各有効成分をそれぞれ計量し、適当な溶剤等に溶解して添加するのが良い。
【００１１】
【作用】
オイルクエンチ塔より留出する塔底油の粘度上昇は、フィード油中に含まれるスチレン，メチルスチレン、ジビニルベンゼン，インデン等、芳香族不飽和化合物の重合に起因すると推定されることから、この重合を抑制できれば、粘度の上昇を抑制可能と考えられる。しかし、従来の重合禁止剤のみでは、効果的な抑制は行えなかった。本発明の粘度上昇抑制剤は、生成した初期重合物に吸着し、これを分散させることにより、重合の進行および生成重合物の分岐，架橋を防止し、粘度の上昇を抑制すると考えられる。
【００１２】
【実施例】
実施例によって、本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。
［テストに用いた薬品］
Ａ，スルフォン酸；ドデシルベンゼンスルフォン酸（分岐型）遊離酸
Ｂ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／テトラデシルアミン塩
ドデシルベンゼンスルフォン酸（分岐型）とテトラデシルアミンを等モルキシレンに溶解し、６０℃にて２時間保ち塩を形成させた。テストにはキシレン溶液そのまま添加した。
以下同様にして塩を得た。
Ｃ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／ヤシアルキルアミン塩
Ｄ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／２−エチルヘキシルアミン塩
Ｅ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／ジブチルアミン塩
Ｆ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／エチレンジアミン塩
Ｇ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（分岐型）／モノエタノールアミン塩
Ｈ，スルフォン酸塩；ドデシルベンゼンスルフォン酸（直鎖型）／テトラデシルアミン塩
Ｉ，スルフォン酸塩；トリデシルベンゼンスルフォン酸（分岐型）／テトラデシルアミン塩
Ｊ，スルフォン酸塩；ｔｅｒｔ−ブチルベンゼンスルフォン酸／ｎ−ブチルアミン塩
Ｋ，スルフォン酸塩；石油スルフォン酸／ナトリウム塩
Ｌ，スルフォン酸塩；ｐ−エチルベンゼンスルフォン酸／ｎ−ブチルアミン塩
４−ｔｅｒｔ−ブチルカテコール（ＴＢＣ）：大日本インキ化学工業株式会社製、ＤＩＣ−ＴＢＣ（商標名）
２，６−ジメチル−ｐ−クレゾール（ＢＨＴ）：川口化学工業株式会社製、アンテージＢＨＴ（商標名）
Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン：住友化学工業株式会社製、スミライザーＢＰＡ（商標名）
ジエチルヒドロキシルアミン：東海電化工業株式会社製、ＤＥＨＡ（商標名）
ジフェニルアミン（ＤＰＡ）：精工化学株式会社製、
ポリメタクリレート系分散剤：分子量１５万〜２０万、テキサコカンパニー製、ＴＣ−８１０３（商標名）
【００１３】
［粗原料］
ドデシルベンゼンスルフォン酸（分岐型）：テイカ株式会社製、テイカパワー Ｂ−１２０（商標名）
ドデシルベンゼンスルフォン酸（直鎖型）：テイカ株式会社製、テイカパワー Ｌ−１２０（商標名）
トリデシルベンゼンスルフォン酸（分岐型）：テイカ株式会社製、テイカパワー Ｂ−１３０（商標名）
石油スルフォン酸ナトリウム塩：株式会社松村石油研究所製、スルホール ５００（商標名）
テトラデシルアミン：日本油脂株式会社製、アミン ＭＢ（商標名）
ヤシアルキルアミン：日本油脂株式会社製、アミン ＦＢ（商標名）
２−エチルヘキシルアミン、ジブチルアミン、エチレンジアミン、モノエタノールアミン、ｎ−ブチルアミン：東京化成株式会社製の試薬を用いた。
【００１４】
［粘度上昇抑制テスト］
２００ｍｌガラス容器に、 試験油１００ｍｌを入れ、所定量の粘度上昇抑制剤を添加した後、恒温槽（１８０℃）に１５時間静置した。冷却後、ＢＬ型回転粘度計（株式会社東京計器社製）により２５℃における粘度の測定を行った。試験油として、実機オイルクエンチ塔塔底油（スチレン ０．１％以下、メチルスチレン ０．１％以下、ジビニルベンゼン ０．１％以下、インデン ０．１％以下含有）と、 塔底油とオイルクエンチ塔リフラックス油（スチレン ３０％、メチルスチレン １４．５％、ジビニルベンゼン ０．２％、インデン ９％含有）の９：１（容積比）混合油とをそれぞれ用いた。それらのテスト結果を表１と表２に示す。
【００１５】
これらの結果より、本発明のスルフォン酸あるいはその塩、さらに重合禁止剤を加えて用いることにより、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇を効率よく抑制できることが認められた。
【００１６】
【発明の効果】
本発明により、オイルクエンチ塔塔底の芳香族不飽和化合物の粘度上昇を抑制することができ、ガソリン収率の向上，ボトムポンプの負荷の軽減、配管内各所での閉塞抑制、オイルクエンチ塔での還流量の削減が可能となる。また、塔底部の温度を上げることが可能となることから、後続プロセスにおける加熱スチーム使用量の削減等、様々な経済的効果が期待できる。[0001]
[Industrial applications]
The present invention, by suppressing the increase in viscosity of the aromatic unsaturated compounds of the oil quench tower bottoms in the olefin production process, improve product yield, improved thermal efficiency, for the purpose of stabilizing such operation, the aromatic The present invention relates to a viscosity rise inhibitor for unsaturated compounds and a method for suppressing viscosity rise.
[0002]
[Prior art]
The production of olefins in the petrochemical industry is usually carried out by pyrolysis of naphtha. Naphtha is pyrolyzed at 800-850 ° C with dilution steam in a pyrolysis furnace, quenched to 350-400 ° C at the cracking furnace outlet, and then sent to an oil quench tower (also called gasoline fractionator or gasoline rectification tower). Here, it is divided into light components having 9 or less carbon atoms and heavy components having more than 9 carbon atoms. The feed oil of the oil quench tower contains aromatic unsaturated compounds such as styrene, methylstyrene, divinylbenzene, and indene, and these compounds are polymerized by heat in the oil quench tower or at the bottom of the tower, This causes an increase in the viscosity of the oil at the bottom of the column, or causes contamination with a polymer in the column. Conventionally, in order to prevent contamination in the tower, the addition of a polymerization inhibitor has been exclusively performed, but this is simply prevention of contamination by polymerization inhibition, and although some effects are recognized, the viscosity of the bottom oil is It is not enough to suppress the rise. Therefore, in order to suppress an increase in the viscosity of the bottom oil, it is common to control the temperature at the bottom of the column to be low to cope with this.
[0003]
[Problems to be solved by the invention]
The problem to be solved is to provide an agent capable of suppressing an increase in the viscosity of an aromatic unsaturated compound at the bottom of an oil quench column and a method thereof in an olefin production process.
[0004]
[Means for Solving the Problems]
The present inventors have found that the viscosity increase of the aromatic unsaturated compound at the bottom of the oil quench tower is caused by the thermal polymerization of aromatic unsaturated compounds such as styrene, methylstyrene, divinylbenzene, and indene contained in the feed oil. As a result of intensive studies on the mechanism of polymerization inhibition and viscosity increase, it was found that a compound capable of suppressing the increase in viscosity of the aromatic unsaturated compound at the bottom of the column was found, and the present invention was completed.
[0005]
That is, the present invention relates to a sulfonic acid represented by the following general formula (I) or a salt thereof (wherein R 1 is an alkyl group having a linear or branched structure having 4 to 32 carbon atoms; or an alkyl-substituted benzene nucleus) Alternatively, in the alkyl-substituted naphthalene nucleus, at least one of the substituted alkyl groups has a linear or branched structure having 4 to 32 carbon atoms, and X represents hydrogen, an alkali metal, an alkaline earth metal, or a C 1 to C 22 metal. A primary, secondary, or tertiary amine salt having a linear or branched structure, which may have a hydroxyl group or an alkoxyl group in the molecule, and n is 1 or 1/2.) It is an agent for increasing the viscosity of an aromatic unsaturated compound at the bottom of an oil quench tower, which is contained as a component. Further aromatic amine-based polymerization inhibitor thereto, phenol-based polymerization inhibitor, one or more selected from dialkylhydroxylamine based polymerization inhibitor, the aromatic compound of the following general formula (I), consists in blending It is a viscosity increase inhibitor for unsaturated compounds .
[0006]
R 1 -SO 3 [X] n . . . (I)
Also, in an oil quench column in a process of producing olefins by pyrolyzing hydrocarbons such as naphtha, light oil, natural gas, and liquefied natural gas as raw materials, the amount of the above-mentioned general oil is reduced with respect to the amount of bottom oil. The viscosity of the aromatic unsaturated compound at the bottom of the oil quench column by adding the agent to the bottom oil so as to maintain the active ingredient of the sulfonic acid of the formula (I) or a salt thereof at 10 ppm to 10,000 ppm. It is intended to provide a method for suppressing a rise.
[0007]
The active ingredient of the present invention is a sulfonic acid represented by the above general formula (I) or a salt thereof, and R 1 is nonyl, dodecyl, octadecyl, a petroleum sulfonic acid residue, dodecylbenzene, tri-decylbenzene, dibutyl. Benzene, octylbenzene, nonylbenzene, and nonylnaphthalene. X is hydrogen; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as magnesium, barium and calcium; propylamine salt, dipropylamine salt, butylamine salt, dibutylamine salt, tributylamine salt; Isobutylamine salt, diisobutylamine salt, sec-butylamine salt, di-sec-butylamine salt, 1,2-dimethylpropylamine salt, hexylamine salt, cyclohexylamine salt, heptylamine salt, 2-ethylhexylamine salt, di- ( 2-ethylhexyl) amine salt, octylamine salt, nonylamine salt, decylamine salt, undecylamine salt, dodecylamine salt, tetradecylamine salt, hexadecylamine salt, octadecylamine salt, cocoalkylamine salt, monoethanolamine Alkylamine salts such as emission salts. Specific examples include sodium dodecylbenzene sulfonate, sodium petroleum sulfonate, cocoalkylamine dodecylbenzenesulfonate, monoethanolamine dodecylbenzenesulfonate, and the like. These sulfonic acids or salts thereof may be used alone or in combination of two or more, and the present invention does not impose any limitation on the mixed use.
[0008]
The polymerization inhibitor of the present invention is generally defined as having the same meaning as an antioxidant based on a radical chain inhibiting action. Examples of the aromatic amine polymerization inhibitor include p-phenylenediamine, N, N′-diamine. -Diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N- (1-methylheptyl) -p-phenylenediamine and the like 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, p-methoxyphenylmethylamine, 4,4'-dinonyldiphenylamine, diphenylamine, phenyl-α-naphthylamine, phenyl And secondary amines such as -β-naphthylamine. Examples of the phenol polymerization inhibitor include phenol, 2-methylphenol, 4-methylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-di-tert-butylphenol, and 2,4-dimethylphenol. Phenols such as di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 2,6-diisopropylphenol, 2,6-dimethyl-4-tert-butylphenol, 4-methoxyphenol; 4-tert-butylcatechol Catechols; and hydroquinones such as hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,5-di-tert-amylhydroquinone. Examples of the dialkylhydroxylamine polymerization inhibitor include diethylhydroxylamine, dipropylhydroxylamine and the like.
[0009]
These polymerization inhibitors may be used alone or in combination of two or more, and the present invention does not impose any restrictions on the mixed use of these polymerization inhibitors.
When the polymerization inhibitor of the present invention is used in combination with sulfonic acid or a salt thereof, the compounding ratio is 10 (weight) times or less of the sulfonic acid of the general formula (I) or a salt thereof.
The addition amount of the viscosity increase inhibitor of the present invention is such that the active ingredient of the sulfonic acid of the above general formula (I) or a salt thereof is 10 ppm to 10,000 ppm, preferably 10 ppm to 2000 ppm, based on the amount of oil at the bottom of the oil quench column. To keep it. If the amount is less than 10 ppm, a sufficient effect cannot be expected. If the amount is more than 10,000 ppm, the effect is sufficient, but the effect is not improved in proportion to the added amount, which is not economically preferable.
[0010]
Although the injection point of the viscosity increase inhibitor of the present invention is not particularly limited, it is usually added to an oil quench tower feed oil or reflux oil, or directly added to an oil quench tower bottom liquid.
In addition, when adding the viscosity increase inhibitor of the present invention, each active ingredient is separately added, or mixed at a predetermined ratio and added. However, from the viewpoint of ease of handling, it is preferable to measure each active ingredient and dissolve it in an appropriate solvent or the like and add it.
[0011]
[Action]
The increase in the viscosity of the bottom oil distilled from the oil quench tower is presumed to be caused by the polymerization of aromatic unsaturated compounds such as styrene, methylstyrene, divinylbenzene, and indene contained in the feed oil. It can be considered that if the viscosity can be suppressed, the increase in viscosity can be suppressed. However, effective suppression could not be achieved only with the conventional polymerization inhibitor. It is considered that the viscosity increase inhibitor of the present invention adsorbs on the produced initial polymer and disperses it, thereby preventing the progress of polymerization and branching and crosslinking of the produced polymer, thereby suppressing the increase in viscosity.
[0012]
【Example】
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[Chemicals used for testing]
A, sulfonic acid; dodecylbenzenesulfonic acid (branched) free acid B, sulfonate; dodecylbenzenesulfonic acid (branched) / tetradecylamine salt dodecylbenzenesulfonic acid (branched) and tetradecylamine in equimolar xylene It was dissolved and kept at 60 ° C. for 2 hours to form a salt. The xylene solution was directly added to the test.
Thereafter, a salt was obtained in the same manner.
C, sulfonate; dodecylbenzenesulfonic acid (branched type) / cocoalkylamine salt D, sulfonate; dodecylbenzenesulfonic acid (branched type) / 2-ethylhexylamine salt E, sulfonate; dodecylbenzenesulfonic acid ( (Branched type) / dibutylamine salt F, sulfonate; dodecylbenzenesulfonic acid (branched type) / ethylenediamine salt G, sulfonate; dodecylbenzenesulfonic acid (branched type) / monoethanolamine salt H, sulfonate; dodecyl Benzenesulfonic acid (linear type) / tetradecylamine salt I, sulfonate; tridecylbenzenesulfonic acid (branched type) / tetradecylamine salt J, sulfonate; tert-butylbenzenesulfonic acid / n-butylamine salt K, sulfonate; petroleum sulfur Sulfonic acid / sodium salt L, sulfonates; p-ethylbenzene sulfonic acid / n-butylamine salt 4-tert-butylcatechol (TBC): manufactured by DIC Corporation, DIC-TBC (trade names)
2,6-Dimethyl-p-cresol (BHT): Antage BHT (trade name) manufactured by Kawaguchi Chemical Industry Co., Ltd.
N, N'-di-sec-butyl-p-phenylenediamine: Sumilizer BPA (trade name) manufactured by Sumitomo Chemical Co., Ltd.
Diethylhydroxylamine: DEHA (trade name) manufactured by Tokai Denka Kogyo Co., Ltd.
Diphenylamine (DPA): manufactured by Seiko Chemical Co., Ltd.
Polymethacrylate dispersant: molecular weight of 150,000 to 200,000, manufactured by Texaco Company, TC-8103 (trade name)
[0013]
[Crude raw material]
Dodecylbenzenesulfonic acid (branched type): manufactured by Teica Co., Ltd., Teica Power B-120 (trade name)
Dodecylbenzenesulfonic acid (linear type): manufactured by Teica Co., Ltd., Teica Power L-120 (trade name)
Tridecylbenzenesulfonic acid (branched type): manufactured by Teica Co., Ltd., Teica Power B-130 (trade name)
Petroleum sulfonate sodium salt: manufactured by Matsumura Petroleum Institute Co., Ltd., Surhol 500 (trade name)
Tetradecylamine: Amine MB (trade name) manufactured by NOF Corporation
Palm alkylamine: Amine FB (trade name) manufactured by NOF Corporation
2-ethylhexylamine, dibutylamine, ethylenediamine, monoethanolamine, n-butylamine: Reagents manufactured by Tokyo Chemical Industry Co., Ltd. were used.
[0014]
[Viscosity rise suppression test]
100 ml of test oil was placed in a 200 ml glass container, a predetermined amount of a viscosity increase inhibitor was added, and the mixture was allowed to stand in a thermostat (180 ° C.) for 15 hours. After cooling, the viscosity at 25 ° C. was measured by a BL-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). As test oils, oil quench tower bottom oil (contains styrene 0.1% or less, methylstyrene 0.1% or less, divinylbenzene 0.1% or less, indene 0.1% or less), and bottom oil and oil A 9: 1 (volume ratio) mixed oil of a quench tower reflux oil (containing 30% of styrene, 14.5% of methylstyrene, 0.2% of divinylbenzene, and 9% of indene) was used. Tables 1 and 2 show the test results.
[0015]
From these results, it was confirmed that the viscosity increase of the aromatic unsaturated compound at the bottom of the oil quench column can be efficiently suppressed by using the sulfonic acid or a salt thereof of the present invention and further adding a polymerization inhibitor.
[0016]
【The invention's effect】
According to the present invention, an increase in the viscosity of the aromatic unsaturated compound at the bottom of the oil quench tower can be suppressed, the gasoline yield can be improved, the load on the bottom pump can be reduced, clogging can be suppressed at various points in the piping, and the oil quench tower can be used. Can be reduced. Further, since it becomes possible to raise the temperature at the bottom of the tower, various economic effects such as a reduction in the amount of heating steam used in the subsequent process can be expected.
Claims (3)
Ｒ1−ＳＯ3［Ｘ］n ．．．（I）
のスルフォン酸、 あるいはその塩類（式中Ｒ1は炭素数４〜３２の直鎖、もしくは分岐構造を有するアルキル基；又はアルキル置換ベンゼン核もしくはアルキル置換ナフタレン核で、置換アルキル基のうち少なくとも１つは炭素数４〜３２の直鎖、もしくは分岐構造を有する。Ｘは水素、アルカリ金属、アルカリ土類金属、又は炭素数１〜２２の直鎖，もしくは分岐構造を有する一級、二級、もしくは三級アミン塩で、分子中にヒドロキシル基、もしくはアルコキシル基をもっていてもよい。ｎは１あるいは１/２である。）の化合物の少なくとも一種を有効成分として含有することを特徴とする、芳香族不飽和化合物の粘度上昇抑制剤。General formula (I)
R 1 -SO 3 [X] n . . . (I)
Or a salt thereof (wherein R 1 is an alkyl group having a linear or branched structure having 4 to 32 carbon atoms; or an alkyl-substituted benzene nucleus or an alkyl-substituted naphthalene nucleus, and at least one of the substituted alkyl groups) Has a linear or branched structure having 4 to 32 carbon atoms, X is hydrogen, an alkali metal, an alkaline earth metal, or a primary, secondary, or tertiary structure having a linear or branched structure having 1 to 22 carbon atoms. in grade salt, characterized by containing as an active ingredient at least one compound of the hydroxyl groups in the molecule, or may have an alkoxyl group .n is 1 or 1/2.), aromatic unsaturated Saturated compound viscosity increase inhibitor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669793A JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
| US08/861,922 US5824829A (en) | 1993-12-16 | 1997-05-22 | Hydrocarbon viscosity inhibitor and inhibiting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669793A JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07166152A JPH07166152A (en) | 1995-06-27 |
| JP3545440B2 true JP3545440B2 (en) | 2004-07-21 |
Family
ID=18079899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31669793A Expired - Lifetime JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3545440B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1295412B1 (en) * | 1997-10-06 | 1999-05-12 | Chimec Spa | COMPOSITION OF ANTI-AGING ADDITIVE FOR QUENCH OIL CIRCUIT IN AN ETHYLENE PRODUCTION PLANT AND METHOD OF OPERATION |
| JP4834250B2 (en) * | 2001-07-31 | 2011-12-14 | 伯東株式会社 | Method for inhibiting polymerization of aromatic vinyl compound |
| US6926820B2 (en) * | 2002-09-20 | 2005-08-09 | G.E. Betz, Inc. | Inhibition of viscosity increase and fouling in hydrocarbon streams including unsaturation |
| JP4686550B2 (en) * | 2005-02-04 | 2011-05-25 | ケムチュア コーポレイション | Means for controlling the exothermic reaction between styrenic monomers and sulfonic acids |
| US8246858B2 (en) * | 2006-03-24 | 2012-08-21 | Hakuto Co., Ltd. | Process for inhibiting polymerization of an aromatic vinyl compound |
| JP5660654B2 (en) * | 2009-05-28 | 2015-01-28 | 伯東株式会社 | Method to prevent soil growth in the gas phase inside an oil quench tower |
| US9505988B2 (en) * | 2011-10-19 | 2016-11-29 | Nalco Company | Circulation aid for primary fractional quench loops |
| US20180155645A1 (en) * | 2016-12-07 | 2018-06-07 | Ecolab Usa Inc. | Antifouling compositions for petroleum process streams |
-
1993
- 1993-12-16 JP JP31669793A patent/JP3545440B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07166152A (en) | 1995-06-27 |
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