CN112679547B - Preparation method of oil-soluble carboxylic acid complex - Google Patents
Preparation method of oil-soluble carboxylic acid complex Download PDFInfo
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- CN112679547B CN112679547B CN202110016221.8A CN202110016221A CN112679547B CN 112679547 B CN112679547 B CN 112679547B CN 202110016221 A CN202110016221 A CN 202110016221A CN 112679547 B CN112679547 B CN 112679547B
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- carboxylic acid
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- water
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 10
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 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
- 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
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims 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 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
- 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- 239000005971 1-naphthylacetic acid Substances 0.000 description 1
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 description 1
- GXXXUZIRGXYDFP-UHFFFAOYSA-N 2-(4-methylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C=C1 GXXXUZIRGXYDFP-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- VIBOGIYPPWLDTI-UHFFFAOYSA-N 2-naphthylacetic acid Chemical compound C1=CC=CC2=CC(CC(=O)O)=CC=C21 VIBOGIYPPWLDTI-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 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
- 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 description 1
- 235000020661 alpha-linolenic acid Nutrition 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000003225 biodiesel Substances 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
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- JWIPDQOXAJMVHL-UHFFFAOYSA-N cyclododecanecarboxylic acid Chemical compound OC(=O)C1CCCCCCCCCCC1 JWIPDQOXAJMVHL-UHFFFAOYSA-N 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent 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
- 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
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 150000004667 medium chain fatty acids Chemical class 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
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 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
- 150000004666 short chain fatty acids Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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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 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 present 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 the advantage of improving the oil solubility and high molybdenum content of the carboxylic acid complex catalyst, providing stable dissolved molybdenum, and not generating solid precipitation due to decomposition, thereby improving and enhancing the 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 increasing reduction of conventional petroleum resources and the increasing maturity of heavy oil exploitation technologies, the production of crude oil has the trend of heavy quality and poor quality. The refining 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 low-quality heavy oil raw materials with high metal, high carbon residue and high sulfur, has high conversion rate and high light oil yield, and accords with an excellent technology for improving the development trend of the resource utilization rate.
The research of heavy oil slurry hydrocracking technology has been carried out by companies abroad, mainly the EST process of Italy ENI company, the HDHPLUS-SHP process developed by Venezuela Intevep in cooperation with French Axens, the VRSH process of Chevron company, the VCC process developed by KBR and BP company, the Uniflex process of UOP company, the (HCAT/HC 3) process of HEADWATER company and the like. The key to the development of the heavy oil slurry bed hydrocracking process is the sustainable progress of high-quality hydrogenation catalysts, wherein the oil-soluble catalysts can be effectively dissolved in heavy raw materials, have excellent hydrogenation effect and can effectively inhibit coking, and are ideal catalysts.
Therefore, the oil-soluble catalyst gradually becomes a research hot spot, and how to obtain the oil-soluble catalyst with simple preparation method and high activity is a technical problem to be solved in the field.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention is directed to a process for the preparation of an oil-soluble carboxylic acid complex.
The aim of the invention is achieved by the following technical scheme: a process for preparing oil-soluble carboxylic acid complex features that the Mo compound and carboxylic acid are directly reacted at high temp with organic amine as catalyst, and water is removed from reaction mixture.
The molybdenum compound adopted by the invention is at least one of ammonium molybdate, molybdic acid, molybdenum trioxide, molybdenum anhydride and molybdenum chloride; the ammonium molybdate is at least one of ammonium mono-molybdate, ammonium di-molybdate and ammonium paramolybdate. In a preferred embodiment of the present invention, ammonium molybdate and molybdic acid are used.
Carboxylic acids contemplated by the present invention are carboxylic acids containing from 4 to 30 carbon atoms, including fatty acids, cycloaliphatic 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, etc.; 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, tetracarboxylic acid, tricarboxylic acid, etc. The alicyclic acid is an alicyclic acid having 4 to 12 carbon atoms such as cyclohexanoic acid, and cyclododecanoic acid. The aromatic acid is an aromatic acid having 7 to 14 carbon atoms, and may contain one or two fused rings, in which the carboxyl group may be attached to the ring or may not be attached to the ring, such as 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, 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 the group consisting of hydrogen, unsubstituted or substituted alkyl of 1 to 10 carbon atoms, and unsubstituted or substituted aryl 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, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Particularly preferred are tertiary alkylamines wherein each alkyl group contains from 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, optimally 1:0.1-0.5.
As previously mentioned, removal of water is a key feature of the process for preparing the oil-soluble carboxylic acid complex 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, stability of the resulting oil-soluble carboxylic acid complex may not be achieved. However, although removal of water 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 water. The 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, a particularly desirable manner involving the use of a gas purge in a conventional manner, including molecular oxygen-containing gases (e.g., air) or inert gases (e.g., nitrogen). 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, allowing for a higher molybdenum content in the resulting oil-soluble carboxylic acid complex. Without sufficient oxygen or air, molybdenum is reduced to form deep blue colloid solutions which can be oxidized by air or oxygen-containing molecular gases at the reaction temperature. In general, an amount of oxygen sufficient to reoxidize reduced lower molybdenum of the reduced molybdenum compound to hexavalent molybdenum may be used.
Or may be removed by using a dehydrating agent (e.g., calcium chloride, sodium sulfate, magnesium sulfate, calcium sulfate, etc.) or by using an entrainer. Any entrainer that is inert to the reaction itself may be used in the process. Suitable azeotroping agents include benzene or aralkyl compounds, such as lower alkylbenzenes containing 1 to 3 alkyl side chains (each alkyl side chain containing 1 to 4 carbon atoms, such as ethylbenzene, xylene and cumene, or alkyl side chains containing 5 to 12 carbon atoms, such as 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 be formed in the reaction, the amount of water removed being dependent upon the desired molybdenum content and reaction time in the carboxylic acid complex produced. 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, with removal of substantially all of the water present or formed during the reaction being the optimal condition to obtain the highest molybdenum content; thus, the water content is not more than 1%, typically about 0.5%, and preferably as low as below 0.1%, based 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, typically in the presence of one or more of the entrainers described above. However, when the carboxylic acid and organic amine used are liquid at the reaction temperature, such solvents are not required.
The reaction temperature of the molybdenum compound and carboxylic acid in the presence of the organic amine should be controlled to be about 150-250 ℃. In a preferred aspect thereof, the reaction is carried out at a temperature of about 170-220 ℃, especially between about 185-210 ℃. Any minimum temperature that provides the desired reaction may be employed, but temperatures above about 250 ℃ are not recommended because the carboxylic acid complex is susceptible to thermal decomposition at such temperatures to form an incompletely homogeneous solution and, therefore, cannot form a stable solution. The use of atmospheric pressure is particularly convenient, but pressures above or below atmospheric pressure may be used if desired. With increasing temperature, shorter reaction times may be employed, although in general, reaction times in the range of about 2 to 36 hours (preferably 10 to 24 hours) or longer are sufficient to produce the desired oil-soluble carboxylic acid complex.
The molar ratio of carboxylic acid to molybdenum compound is 1:4-12, and preferably between about 1:6-8 (on a molar basis). In general, the oil-soluble carboxylic acid complexes of the invention obtained by the above-described process 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 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 present 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 the advantage of improving the oil solubility of the carboxylic acid complex and the high molybdenum content, providing stable dissolved molybdenum, without generating solid precipitation due to decomposition, thereby improving and enhancing the oil-soluble carboxylic acid complex preparation and productivity.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
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, the contents thereof were continuously stirred while removing water formed during the reaction, thereby obtaining an oil-soluble carboxylic acid complex. To the carboxylic acid complex prepared above, 20ml of ethylbenzene was added to obtain a homogeneous solution having a molybdenum content of 6%. This solution does not form a precipitate even when left in 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 ℃ and stirred continuously for 10 hours while removing water formed during the reaction. When 20ml of ethylbenzene was added to the carboxylic acid complex prepared above, a large amount of precipitate formed. After filtration of the precipitate, the molybdenum content of the solution was about 35 wt.%, and when the solution was left in air for one month, a large amount of sludge precipitate formed.
Examples 2 to 9
The oil-soluble carboxylic acid complex of the following example was prepared by using the corresponding 4.0 parts of organic amine listed in the following table, instead of 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 amines | Characterization of the solution product diluted with 20ml of ethylbenzene |
| 2 | Di-n-butylamine | Homogeneous phase |
| 3 | N-hexylamine | Homogeneous phase |
| 4 | Hexamethylenediamine | Slight precipitation |
| 5 | Aniline | Homogeneous phase |
| 6 | Diphenylamine | Homogeneous phase |
| 7 | Triphenylamine | Homogeneous phase |
| 8 | Benzylamine | Homogeneous phase |
| 9 | Dibenzylamine | Homogeneous phase |
From the above table, it can be seen that the present invention has advantages in that it enhances the oil solubility of the carboxylic acid complex and the high molybdenum content, provides stable dissolved molybdenum, does not cause solid precipitation due to decomposition, and thus improves and enhances the oil-soluble carboxylic acid complex preparation and productivity.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (2)
1. A process for the preparation of an oil-soluble carboxylic acid complex characterized by: directly reacting a molybdenum compound with carboxylic acid at a high temperature in the presence of an organic amine as a catalyst while removing water from the reaction mixture to produce an oil-soluble carboxylic acid complex; the organic amine comprises at least one of n-hexylamine, triethylamine, diethylamine, dibutylamine, tributylamine, hexamethylenediamine, aniline, diphenylamine, triphenylamine, benzylamine, dibenzylamine, pyridine, alpha-pyridine and piperidine; the reaction temperature is 150-250 ℃ and the reaction time is 2-36h; the molar ratio of carboxylic acid to molybdenum compound is 1:4-12, and the molar ratio of carboxylic acid to organic amine is 1:0.05-1.0; the molybdenum compound is ammonium molybdate and the carboxylic acid is naphthenic acid.
2. The method for producing an oil-soluble carboxylic acid complex according to claim 1, characterized in that: removing water from the reaction mixture using a dehydrating agent or an entrainer; 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.
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