CN112679547A - Preparation method of oil-soluble carboxylic acid complex - Google Patents
Preparation method of oil-soluble carboxylic acid complex Download PDFInfo
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- CN112679547A CN112679547A CN202110016221.8A CN202110016221A CN112679547A CN 112679547 A CN112679547 A CN 112679547A CN 202110016221 A CN202110016221 A CN 202110016221A CN 112679547 A CN112679547 A CN 112679547A
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- China
- Prior art keywords
- acid
- carboxylic acid
- oil
- soluble carboxylic
- carbon atoms
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Links
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 11
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 150000004667 medium chain fatty acids Chemical class 0.000 claims description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 150000004666 short chain fatty acids Chemical class 0.000 claims description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005971 1-naphthylacetic acid Substances 0.000 claims description 2
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 claims description 2
- GXXXUZIRGXYDFP-UHFFFAOYSA-N 2-(4-methylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C=C1 GXXXUZIRGXYDFP-UHFFFAOYSA-N 0.000 claims description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 2
- VIBOGIYPPWLDTI-UHFFFAOYSA-N 2-naphthylacetic acid Chemical compound C1=CC=CC2=CC(CC(=O)O)=CC=C21 VIBOGIYPPWLDTI-UHFFFAOYSA-N 0.000 claims description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 2
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000003225 biodiesel Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- NJRWLESRYZMVRW-UHFFFAOYSA-N carboxy carboxyoxycarbonyl carbonate Chemical compound OC(=O)OC(=O)OC(=O)OC(O)=O NJRWLESRYZMVRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- AXXBSLWCWNGFPM-UHFFFAOYSA-N cyclodecanecarboxylic acid Chemical compound OC(=O)C1CCCCCCCCC1 AXXBSLWCWNGFPM-UHFFFAOYSA-N 0.000 claims description 2
- JWIPDQOXAJMVHL-UHFFFAOYSA-N cyclododecanecarboxylic acid Chemical compound OC(=O)C1CCCCCCCCCCC1 JWIPDQOXAJMVHL-UHFFFAOYSA-N 0.000 claims description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims description 2
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 17
- 239000011733 molybdenum Substances 0.000 abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of petrochemical industry, in particular to a preparation method of an oil-soluble carboxylic acid complex. The present invention produces novel oil-soluble carboxylic acid complexes by the direct reaction of molybdenum compounds with carboxylic acids in the presence of organic amines with removal of water at specific elevated temperatures, and is particularly suitable for use as hydrogenation catalysts. A key feature of the process is the removal of free water during the reaction, which includes any water that may be initially present, as well as water that may be formed during the reaction. The present invention has advantages of improving oil solubility and high molybdenum content of carboxylic acid complex catalyst, providing stable dissolved molybdenum, not generating solid precipitation due to decomposition, thereby improving and enhancing oil-soluble carboxylic acid complex preparation and productivity.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a preparation method of an oil-soluble carboxylic acid complex.
Background
At present, with the decreasing of conventional petroleum resources and the increasing maturity of heavy oil extraction technologies, the production of crude oil tends to be heavy and inferior. The refining and chemical enterprises face the problem of lightening a large amount of domestic inferior heavy oil and imported inferior heavy oil. Meanwhile, the requirements of environmental protection indexes are considered, the quality of gasoline and diesel oil is controlled, and the requirement of producing clean fuel is met. The slurry bed hydrocracking technology can process the inferior heavy oil raw material with high metal content, high carbon residue and high sulfur, has high conversion rate and high light oil yield, and accords with the excellent process for improving the development trend of resource utilization rate.
The research on the hydrocracking technology of heavy oil slurry bed is carried out by various foreign companies, mainly including EST process of ENI company in Italy, HDHPLUS-SHP process developed by Intepep in Venezuela and Axens in France, VRSH process developed by Chevron company, VCC process developed by KBR and BP company, Uniflex process of UOP company and (HCAT/HC3) process of Headwater company. The key point of the development of the heavy oil slurry bed hydrocracking process lies in the continuous progress of a high-quality hydrogenation catalyst, wherein the oil-soluble catalyst can be effectively dissolved in a heavy raw material, has an excellent hydrogenation effect, can effectively inhibit coking, and is an ideal catalyst.
Therefore, the oil-soluble catalyst is gradually a hot point of research, and how to obtain the oil-soluble catalyst with simple preparation method and high activity is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a method for preparing an oil-soluble carboxylic acid complex.
The purpose of the invention is realized by the following technical scheme: a process for preparing oil-soluble carboxylic acid complex features that the molybdenum compound and carboxylic acid are directly reacted at high temp in the presence of organic amine as catalyst while removing water from the reaction mixture.
The molybdenum compound adopted by the invention is at least one of ammonium molybdate, molybdic acid, molybdenum trioxide, molybdic anhydride and molybdenum chloride; the ammonium molybdate is at least one of ammonium mono-molybdate, ammonium dimolybdate and ammonium paramolybdate. In a preferred embodiment of the invention, ammonium molybdate is used together with molybdic acid.
Carboxylic acids contemplated by the present invention are carboxylic acids containing 4 to 30 carbon atoms, including fatty acids, alicyclic acids, and aromatic acids. The fatty acid may be a short chain fatty acid having 2 to 6 carbon atoms, such as butyric acid, isobutyric acid, valeric acid, caproic acid, and the like; or medium chain fatty acids having 7 to 11 carbon atoms, such as caprylic acid, capric acid, sebacic acid, and the like; or long chain fatty acids containing 12 to 30 carbon atoms, such as oleic acid, linoleic acid, palmitic acid, non-biodiesel, linolenic acid, lauric acid, palmitic acid, tetracarbonic acid, tricarbonic acid, and the like. The alicyclic acid is an alicyclic acid having 4 to 12 carbon atoms, such as cyclohexanoic acid, cyclodecanoic acid, cyclododecanoic acid, and the like. The aromatic acid is an aromatic acid having 7 to 14 carbon atoms and may contain one or two fused rings, wherein the carboxyl group may or may not be attached to the ring, such as benzoic acid, 1-naphthoic acid, 2-naphthoic acid, o-tolylacetic acid, m-tolylacetic acid, p-tolylacetic acid, phenylacetic acid, 1-naphthylacetic acid, 2-naphthylacetic acid, phenylbutyric acid, and the like.
The structural formula of the organic amine adopted by the invention is as follows:
wherein each of R1, R2, and R3 is independently selected from hydrogen, an unsubstituted or substituted alkyl group of 1 to 10 carbon atoms, and an unsubstituted or substituted aryl group of 6 to 12 carbon atoms; and at least one of R1, R2, and R3 is not hydrogen.
The above organic amine is preferably each of R1, R2 and R3 is independently selected from hydrogen or unsubstituted alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. Particularly preferred are tertiary alkylamines, wherein each alkyl group contains 1 to 4 carbon atoms. Illustrative are aliphatic amines such as n-hexylamine, triethylamine, diethylamine, dibutylamine, tributylamine, hexamethylenediamine, etc., and aromatic amines such as aniline, diphenylamine, triphenylamine, benzylamine, dibenzylamine, etc.; cyclic amines such as pyridine, alpha-pyridine, piperidine and the like may also be used in the process of the present invention. The molar ratio of carboxylic acid to organic amine is 1: 0.05-1.0, preferably 1: 0.1-0.5.
As previously mentioned, the removal of water is a key feature of the process for the preparation of the oil-soluble carboxylic acid complexes of the present invention. If the reaction is carried out without removing water, a very long reaction time may be required in preparing the oil-soluble carboxylic acid complex, and more importantly, the stability of the resulting oil-soluble carboxylic acid complex may not be achieved. However, while water removal appears to be necessary, the manner in which the water is removed is not important. Thus, during this preliminary reaction, any known technique may be used to remove the water. Water can be removed from the reaction mixture and the reaction time to form the desired oil-soluble carboxylic acid complex can be significantly reduced, with particularly desirable approaches involving the use of gas purges, including molecular oxygen-containing gases (e.g., air) or inert gases (e.g., nitrogen), in conventional fashion. It is particularly preferred to use a molecular oxygen-containing gas, such as purge air, which not only removes water from the reaction mixture, but also maintains the dissolved molybdenum in its higher oxidation state, thereby allowing for a higher molybdenum content in the resulting oil-soluble carboxylic acid complex. In the absence of sufficient oxygen or air, molybdenum is reduced to form dark blue colloidal solutions that can be oxidized by air or molecular oxygen-containing gases at reaction temperatures. Generally, an amount of oxygen sufficient to reoxidize the reduced lower molybdenum of the reduced molybdenum compound to hexavalent molybdenum may be used.
Alternatively, the water may be removed by using a dehydrating agent (e.g., calcium chloride, sodium sulfate, magnesium sulfate, calcium sulfate, etc.) or by using an azeotropic agent. Any entrainer that is inert to the reaction itself may be used in this process. Suitable entrainers include benzene or aralkyl compounds such as lower alkyl benzenes having 1 to 3 alkyl side chains (each alkyl side chain having 1 to 4 carbon atoms, e.g. ethylbenzene, xylene and cumene; or alkyl side chains having 5 to 12 carbon atoms, e.g. hexane, octane and decane). The amount of entrainer required depends on the amount of water to be removed and varies from system to system, and can be readily determined by one skilled in the art. In general, it may not be necessary to completely remove all of the water present or that may have formed during the reaction, the amount of water removed depending on the desired molybdenum content in the carboxylic acid complex produced and the reaction time. The higher the molybdenum content of the carboxylic acid complex produced in the reaction, the greater the amount of water that needs to be removed, and the removal of almost all the water present or formed during the reaction is the optimal condition for obtaining the highest molybdenum content; thus, the water content is not more than 1%, usually about 0.5%, and preferably as low as 0.1% or less, depending on the mass of the reaction mixture.
The molybdenum compound, carboxylic acid and organic amine may generally be reacted in the presence of an inert solvent, which is typically present with one or more of the foregoing entrainers. However, such solvents are not required when the carboxylic acid and the organic amine used are liquid at the reaction temperature.
The reaction temperature of the molybdenum compound and the carboxylic acid in the presence of the organic amine is controlled to be about 150 ℃ and 250 ℃. In a preferred aspect thereof, the reaction is carried out at a temperature of about 170 ℃ and 220 ℃, particularly between about 185 ℃ and 210 ℃. Any minimum temperature that provides the desired reaction may be used, but temperatures above about 250 ℃ are not recommended because the carboxylic acid complex is susceptible to thermal decomposition at this temperature, forming a solution that is not completely homogeneous, and therefore, does not form a stable solution. It is particularly convenient to use atmospheric pressure, but pressures above or below atmospheric pressure may be used if desired. Shorter reaction times may be employed as the temperature is increased, although in general, reaction times in the range of about 2 to 36 hours (preferably 10 to 24 hours) or more will be sufficient to produce the desired oil-soluble carboxylic acid complex.
The molar ratio of carboxylic acid to molybdenum compound is 1:4 to 12, and preferably between about 1:6 to 8 (on a molar basis). In general, the oil-soluble carboxylic acid complex of the present invention obtained by the above-described method may contain molybdenum in an amount of about 5 to 15% by weight, based on the mass of the composition.
The invention has the beneficial effects that: the present invention produces novel oil-soluble carboxylic acid complexes by the direct reaction of molybdenum compounds with carboxylic acids in the presence of organic amines with removal of water at specific elevated temperatures, and is particularly suitable for use as hydrogenation catalysts. A key feature of the process is the removal of free water during the reaction, which includes any water that may be initially present, as well as water that may be formed during the reaction.
The present invention has advantages of improving oil solubility of carboxylic acid complex and high molybdenum content, providing stable dissolved molybdenum, not generating solid precipitation due to decomposition, thereby improving and enhancing preparation and productivity of oil-soluble carboxylic acid complex.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A mixture of 5.5 parts of ammonium molybdate, 18.5 parts of naphthenic acid and 4.0 parts of tri-n-butylamine was heated at 200 ℃ for 10 hours while continuously stirring the contents thereof and removing water formed during the reaction, thereby obtaining an oil-soluble carboxylic acid complex. 20ml of ethylbenzene was added to the carboxylic acid complex prepared above to obtain a homogeneous solution containing 6% of molybdenum. This solution does not form a precipitate even after being left in the air for one month.
Comparative example 1
A mixture of 5.5 parts ammonium molybdate and 22.5 parts naphthenic acid was heated to 200 c and stirring was continued for 10 hours while removing the water formed during the reaction. When 20ml of ethylbenzene was added to the carboxylic acid complex prepared above, a large amount of precipitate was formed. After filtering the precipitate, the molybdenum content of the solution was about 35% by weight, and when the solution was left in air for one month, a large amount of sludge precipitate was formed.
Examples 2 to 9
The oil-soluble carboxylic acid complexes of the following examples were prepared by using the corresponding 4.0 parts of organic amines listed in the following table, instead of the tri-n-butylamine used in example 1. The reaction conditions for preparing these carboxylic acid complexes were the same as in example 1 except that tri-n-butylamine was replaced with other organic amines.
| Examples | Organic amine | Product characteristics of solution diluted with 20ml ethylbenzene |
| 2 | Di-n-butylamine | Homogeneous phase |
| 3 | N-hexylamine | Homogeneous phase |
| 4 | Hexamethylene diamine | Slight precipitation |
| 5 | Aniline | Homogeneous phase |
| 6 | Diphenylamine | Homogeneous phase |
| 7 | Triphenylamine | Homogeneous phase |
| 8 | Benzylamine | Homogeneous phase |
| 9 | Dibenzylamine | Homogeneous phase |
As can be seen from the above table, the present invention is advantageous in that the oil solubility and high molybdenum content of the carboxylic acid complex are improved, stable dissolved molybdenum is provided, solid precipitation due to decomposition is not generated, and thus the preparation and productivity of the oil-soluble carboxylic acid complex are improved and enhanced.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A method for preparing an oil-soluble carboxylic acid complex, characterized by: the oil-soluble carboxylic acid complex is prepared by directly reacting a molybdenum compound with a carboxylic acid in the presence of an organic amine catalyst at high temperature while removing water from the reaction mixture.
2. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the molybdenum compound is at least one of ammonium molybdate, molybdic acid, molybdenum trioxide, molybdic anhydride and molybdenum chloride; the ammonium molybdate is at least one of ammonium mono-molybdate, ammonium dimolybdate and ammonium paramolybdate.
3. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the carboxylic acid is at least one of a fatty acid, an alicyclic acid and an aromatic acid containing 4 to 30 carbon atoms.
4. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the carboxylic acid is at least one of a short-chain fatty acid having 2 to 6 carbon atoms, a medium-chain fatty acid having 7 to 11 carbon atoms, a long-chain fatty acid having 12 to 30 carbon atoms, an alicyclic acid having 4 to 12 carbon atoms, and an aromatic acid having 7 to 14 carbon atoms.
5. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the short-chain fatty acid is at least one of butyric acid, isobutyric acid, valeric acid and caproic acid; the medium-chain fatty acid is at least one of caprylic acid, capric acid and sebacic acid; the long-chain fatty acid is at least one of oleic acid, linoleic acid, palmitic acid, non-biodiesel, linolenic acid, dodecanoic acid, hexadecanoic acid, tetracarbonic acid and tricarbonic acid; the alicyclic acid is at least one of cyclohexanoic acid, cyclodecanoic acid and cyclododecanoic acid; the aromatic acid is at least one of benzoic acid, 1-naphthoic acid, 2-naphthoic acid, o-methylphenylacetic acid, m-methylphenylacetic acid, p-methylphenylacetic acid, phenylacetic acid, 1-naphthylacetic acid, 2-naphthylacetic acid and phenylbutyric acid.
6. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the organic amine has the structural formula:
wherein each of R1, R2, and R3 is independently selected from hydrogen, an unsubstituted or substituted alkyl group of 1 to 10 carbon atoms, and an unsubstituted or substituted aryl group of 6 to 12 carbon atoms; and at least one of R1, R2, and R3 is not hydrogen.
7. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the organic amine has the structural formula:
wherein each of R1, R2, and R3 is independently selected from hydrogen or unsubstituted alkyl.
8. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the organic amine includes at least one of n-hexylamine, triethylamine, diethylamine, dibutylamine, tributylamine, hexamethylenediamine, aniline, diphenylamine, triphenylamine, benzylamine, dibenzylamine, pyridine, α -pyridine, and piperidine.
9. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: removing water from the reaction mixture with a dehydrating agent or an azeotropic agent; the dehydrating agent is at least one of calcium chloride, sodium sulfate, magnesium sulfate and calcium sulfate; the entrainer is at least one of ethylbenzene, xylene, cumene, hexane, octane and decane.
10. The method for producing an oil-soluble carboxylic acid complex according to claim 1, wherein: the reaction temperature is 150-250 ℃, and the reaction time is 2-36 h; the molar ratio of the carboxylic acid to the molybdenum compound is 1:4-12, and the molar ratio of the carboxylic acid to the organic amine is 1: 0.05-1.0.
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