CN116444531A - Method for catalyzing and desulfurizing amphiphilic cobalt phthalocyanine and application - Google Patents
Method for catalyzing and desulfurizing amphiphilic cobalt phthalocyanine and application Download PDFInfo
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- CN116444531A CN116444531A CN202310377288.3A CN202310377288A CN116444531A CN 116444531 A CN116444531 A CN 116444531A CN 202310377288 A CN202310377288 A CN 202310377288A CN 116444531 A CN116444531 A CN 116444531A
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- aeo
- thiophene
- phthalocyanine
- cobalt
- cobalt phthalocyanine
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- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000003009 desulfurizing effect Effects 0.000 title description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical class C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 36
- 230000023556 desulfurization Effects 0.000 claims abstract description 36
- 229930192474 thiophene Chemical class 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000005580 one pot reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000187654 Nocardia Species 0.000 description 1
- 241000316848 Rhodococcus <scale insect> Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000589634 Xanthomonas Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- -1 aromatic sulfides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing and removing organic sulfur by using water/oil amphiphilic cobalt phthalocyanine and application thereof, wherein AEO-7 cobalt phthalocyanine is used as a catalyst, oxygen in air is used as an oxidant according to the structure and catalytic oxidation mechanism of substituted cobalt phthalocyanine, and thiophene in a simulated oil product is removed. The method comprises the following three steps: (1) synthesizing the AEO-7 cobalt phthalocyanine by a one-pot method. Firstly synthesizing a precursor of AEO-7 cobalt phthalocyanine in a reactor, then adding other raw materials to synthesize the AEO-7 cobalt phthalocyanine, and separating and purifying a product; (2) chromatography. Preparing a series of concentration solutions (c) of thiophene, measuring the integral area (S) of the thiophene under a set chromatographic condition, and making a relation curve of S and c to obtain a linear equation. (3) catalytic desulfurization. Adding catalytic amount of AEO-7 cobalt phthalocyanine into a certain volume of thiophene/normal hexane solution with a certain concentration, stirring at normal temperature, and carrying out catalytic desulfurization for 3 hours, wherein the removal rate of thiophene is more than 90%. The AEO-7 cobalt phthalocyanine is a novel catalytic material, has water/oil amphiphilicity, and has higher efficiency of catalyzing out thiophene.
Description
Technical Field
The invention belongs to the field of catalytic materials, and relates to a novel desulfurization catalyst based on phthalocyanine structure and property. The catalyst is used for oxidizing and removing sulfur-containing components in oil products by catalytically activating oxygen in air, and is suitable for removing organic sulfur which is difficult to remove in the oil products.
Background
Sulfides, especially organic sulfides, are one of the main impurities in petroleum, and the sulfur content in petroleum is 0.5% -4%. Common organosulfur compounds are thiols, sulfides, disulfides, thiophenes, benzothiophenes, dibenzothiophenes, and the like. Sulfur removal techniques include hydrogenation, adsorption, oxidation, biological desulfurization, and the like.
Hydrodesulfurization is a relatively mature desulfurization technology which is widely applied in industry at present, and the technology is that sulfide reacts with hydrogen to generate hydrogen sulfide and hydrocarbon substances under the condition of high temperature and high pressure in the presence of a catalyst. However, for heterocyclic compounds, such as thiophene, dibenzothiophene and 4, 6-dimethyldibenzothiophene, the heterocyclic compounds are difficult to be carried out under extreme process conditions, which means that the requirements on industrial equipment are high, the input cost is high, and correspondingly, more potential safety hazards are caused.
Adsorption desulfurization is to remove sulfides by using an adsorbent, is a low-temperature and low-pressure technology, and is a good alternative way of hydrodesulfurization. In general, the adsorbents used have more mesopores and surface active centers, as well as good structural strength and stability. The adsorption desulfurization is to maintain high desulfurization efficiency, and a key problem is that the adsorbent is easy to overload when treating high sulfur-containing raw materials, so that the regeneration and service life of the adsorbent become bottleneck problems for industrial application. Common adsorbent materials are zeolites, carbon materials, metal organic frameworks, and the like.
Extraction desulfurization, which is a simple way of extracting aromatic sulfides from petroleum fractions using an extractant under mild operating conditions, is a simple way of desulfurizing the petroleum fractions. The basis is that the solubility of sulfur compounds and aromatic hydrocarbons in properly polar solvents is better than that of non-aromatic hydrocarbons. The method does not change the chemical structure of the compound and does not affect the quality of the liquid fuel. There are problems in that the desulfurization rate of the extractive desulfurization is not ideal, particularly, in the case of high sulfur oil, it is difficult to achieve the requirement of 10ppm or less, and in addition, the recycling rate of the extractant is a great challenge. Extraction desulfurization is often combined with other desulfurization modes to achieve the effect of deep desulfurization.
Biological desulfurization refers to a green method for removing sulfides in living organism catalytic fuel oil. This is an environmentally friendly process with mild application conditions, high selectivity, low cost, low emissions, and no undesirable byproducts and no chemicals added. Common strains are rhodococcus, xanthomonas, nocardia, mycobacteria, and the like. While this is a green and economical process that helps reduce carbon dioxide emissions, its industrial application is limited by the low kinetic efficiency of the related microbial enzyme catalysis.
In contrast, oxidative desulfurization operations are not only mild in conditions, but also easy to separate the oxidized sulfidic products, and are generally considered to be the best desulfurization technique. Common oxidants for oxidative desulfurization are NOX, H202, O2, etc., with molecular oxygen in the environment being the most promising and advantageous, and obviously air oxygen is safe, inexpensive and environmentally friendly. Due to its excellent catalytic properties, metal phthalocyanines have been used by numerous researchers in the field of oxidative desulfurization. Cobalt phthalocyanine can be used as a catalyst for oxidizing thiophene sulfides. In contrast, cobalt phthalocyanine catalytic desulfurization has been studied more, wherein the kind of substituent has a great influence on the dispersibility and catalytic performance of cobalt phthalocyanine. Based on the requirement of catalytic desulfurization of oil products, the invention synthesizes AEO-7 cobalt phthalocyanine with water/oil amphiphilicity by a one-pot method, which is used for desulfurizing an organic phase, and then washing out the phthalocyanine by water so as to achieve the purpose of high-efficiency desulfurization.
Disclosure of Invention
(one) the object of the invention: one-pot synthesis of AEO-7 cobalt phthalocyanine desulfurizing catalyst with water-oil amphiphilicity is suitable for organic phase catalytic desulfurizing.
(II) technical scheme: the technical proposal is as follows.
(1) In a reactor, 4-nitrophthalonitrile is taken as a substrate, AEO-7 is added, under the condition of taking lithium hydroxide as a catalyst, a para-phthalocyanine precursor is synthesized, and then cobalt chloride, ammonium molybdate and urea are added to react at 190 ℃ to obtain AEO-7 cobalt phthalocyanine, the product is dissolved in water and then extracted twice by using ethyl acetate with the same volume, several phases are combined, the phases are washed with water for 2 times, an organic phase is dried by anhydrous sodium sulfate, and the solvent is evaporated by rotary evaporation of the organic phase to obtain blue solid cobalt phthalocyanine.
(2) Preparing normal hexane solution of thiophene with a certain concentration, placing the normal hexane solution into a beaker, adding catalytic amount of AEO-7 cobalt phthalocyanine, stirring and reacting at normal temperature and normal pressure, sampling once every certain time, washing the catalyst, filtering an organic phase by using a filter membrane (0.2 mu m), sampling and sampling, and analyzing by chromatography, thus obtaining the removal rate of the thiophene.
(III) advantages and effects
(1) The catalyst is simple to synthesize, separate and purify. The one-pot process synthesizes the water/oil amphiphilic AEO-7 cobalt phthalocyanine desulfurizing catalyst, and the separation and purification process is extraction.
(2) The removal of organic sulfur can often be effected at temperature. Thiophene is used as an organic sulfur component, normal hexane solution of the thiophene is prepared, AEO-7 cobalt phthalocyanine is added, stirring and desulfurization are carried out at normal temperature, and the desulfurization rate is more than 90 percent after 3 hours.
Detailed Description
Example 1
One of the one-pot synthesis of AEO-7 cobalt phthalocyanine: one of the one-pot syntheses of AEO-7 iron phthalocyanine: in a 250mL beaker, 20mL of DMSO was added as a solvent, stirred magnetically, 1.73g of 4-nitrophthalonitrile and 4.94g of AEO-7 were added, a total of 0.42g of LiOH H2O was added in two portions, and stirred at room temperature for 24H. The progress of the reaction was checked by thin layer chromatography, with petroleum ether: ethyl acetate=1:3 (V: V). After the reaction, coCl is added into the reaction system 2 ·6H 2 O, mass 0.595g, urea 3g and ammonium molybdate 0.1g were added. The beaker mouth was covered with a 250mL round bottom flask and then heated at 190 ℃ for 2h.
After cooling down, add 100mL of water to dissolve the reaction mass, filter, extract the filtrate with 100mL of ethyl acetate for 2 times, combine the extracts, wash with distilled water for 2 times, dry the organic phase over night with a proper amount of anhydrous sodium sulfate, evaporate the solvent from the dried organic phase by spin to give 4.82g of blue solid AEO-7 iron phthalocyanine with a yield of 76%.
Example 2
Two-pot synthesis of AEO-7 cobalt phthalocyanine: as in example 1, if 20mL of DMF was initially used as solvent instead of DMSO, the other reaction conditions were unchanged and AEO-7 cobalt phthalocyanine was synthesized by a one-pot method. Finally, 4.97g of blue solid AEO-7 cobalt phthalocyanine is obtained, and the yield is 78.3%.
Example 3
Three-pot synthesis of cobalt AEO-7 phthalocyanine: as in example 1, if 20mL of THF was initially used as solvent instead of DMSO, the other reaction conditions were unchanged and AEO-7 cobalt phthalocyanine was synthesized by a one-pot method. 4.35g of blue solid AEO-7 cobalt phthalocyanine is finally obtained, and the yield is 68.6%.
Example 4
Chromatographic analysis method: n-hexane solutions of 2%, 1.5%, 1%, 0.5% and 0.2% thiophene were prepared, respectively, and analyzed by gas chromatography. 2. Mu.L of sample is introduced, the sample introduction temperature is 250 ℃, the detection temperature is 280 ℃, and the temperature rise program of a chromatographic column (SE-30, 30m multiplied by 0.32mm multiplied by 0.33 μm) is 50 ℃, 6min, 30 ℃/min, 1.5min and thiophene retention time is 2.4min. And (5) according to the analysis result, a curve of the concentration c and the integral area S is made, and an integral equation is obtained. S=4775694.27c+85.145, r 2 ＝0.9997。
Example 5
Desulfurization operation one: 50mL of a thiophene normal hexane solution with a concentration of 2% was prepared, added to a 100mL beaker, 0.01g of AEO-7 cobalt phthalocyanine was added, the mixture was stirred at normal temperature and normal pressure to react, samples were taken every 30min, 2mL of the mixture was taken, water was washed, and the organic phase was filtered 2 times with a filter (0.2 μm) and analyzed by 2. Mu.l of sample injection. After 1h, the residual thiophene concentration was 53.8%, and the thiophene removal rate was 46.2%. After 3h, the thiophene removal rate was 93.7%.
Example 6
Desulfurization operation two: 100mL of a thiophene-containing n-hexane solution having a concentration of 2% was prepared, and 0.012g of AEO-7 cobalt phthalocyanine was added to a 250mL beaker, followed by desulfurization reaction under stirring at normal temperature and pressure. After 3h, 2mL of sample was taken, washed with water, the organic phase was filtered 2 times through a filter (0.2 μm), and 2. Mu.L of sample was analyzed, and the thiophene removal rate was 94.1%.
Example 7
As in example 6, 1.88mL of thiophene was added to the reaction system after 3 hours of desulfurization to recover the concentration of the thiophene solution to 2%, stirring was continued at room temperature for 3 hours, and the removal rate of thiophene was 93.5% by chromatographic analysis.
Example 8
As in example 7, 1.87mL of thiophene was added to the reaction system after 3 hours of desulfurization to recover the concentration of the thiophene solution to 2%, stirring was continued at room temperature for 3 hours, and the removal rate of thiophene was 92.7% by chromatographic analysis.
Claims (6)
1. The method for catalytic desulfurization of water/oil double-soluble cobalt phthalocyanine and the application thereof are characterized by comprising the following steps:
(1) One-pot synthesis of AEO-7 cobalt phthalocyanine, adding theoretical equimolar amounts of AEO-7, 4-nitrophthalonitrile and LiOH H into a beaker at normal temperature 2 O and a proper amount of solvent, and stirring for 24 hours; adding other CoCl for synthesizing phthalocyanine into the reaction system 2 ·7H 2 O, urea and ammonium molybdate, heating at 190 ℃ for 2h at constant temperature; after the reactants are cooled, adding a proper amount of distilled water for dissolution, then extracting for 2 times by using an equal volume of ethyl acetate, combining the extracts, washing for 2 times by using distilled water, drying an organic phase by using anhydrous sodium sulfate, and evaporating a solvent by rotary evaporation to obtain blue solid AEO-7 cobalt phthalocyanine.
(2) And (3) performing chromatographic analysis, namely respectively preparing thiophene/n-hexane solutions with serial concentrations, and performing gas chromatographic analysis to obtain a relation curve of the integrated area and the concentration of the thiophene and a relation formula.
(3) And (3) performing catalytic removal on thiophene by using the AEO-7 cobalt phthalocyanine, preparing a solution with a certain concentration by using the AEO-7 cobalt phthalocyanine obtained in the step (1), adding the solution into a certain amount of thiophene/normal hexane solution with a certain concentration prepared in the step (2), stirring a desulfurization system at normal temperature, performing catalytic activation on oxygen in air to remove thiophene, and periodically sampling and analyzing the concentration of thiophene in the solution.
2. The method for cobalt-catalyzed removal of thiophenic sulfur according to claim 1, wherein in said step (1), AEO-7, 4-nitrophthalonitrile, liOH. H 2 O、CoCl 2 ·7H 2 The molar ratio of O, urea and ammonium molybdate is 1:1:1:0.25:5:0.05, the solvent is DMSO or DMF or THF, and the ratio of the volume of the solvent to the sum of the masses of AEO-7 and 4-nitrophthalonitrile is 3:1 (mL: g).
3. The method for catalytic desulfurization of cobalt AEO-7 phthalocyanine according to claim 1, characterized in that in said step (1), the cobalt AEO-7 phthalocyanine is soluble in water and more soluble in ethyl acetate, and is characterized by an absorption wavelength of 622nm.
4. The method for catalytic desulfurization of cobalt AEO-7 phthalocyanine according to claim 1, characterized in that in said step (2), 2 μl is injected, the injection temperature is 250 ℃, the detection temperature is 280 ℃, the temperature program of the chromatographic column (SE-30, 30m×0.32mm×0.33 μm) is 50 ℃, 6min, 30 ℃/min, 1.5min, thiophene retention time is 2.4min. And (5) according to the analysis result, a curve of the concentration c and the integral area S is made, and an integral equation is obtained. S=4775694.27c+85.145, r 2 ＝0.9997。
5. The method for catalytic removal of thiophenic sulfur from cobalt AEO-7 phthalocyanine according to claim 1, wherein in said step (3), the concentration of thiophenic in 50,100 mL of desulfurization solution is 2%, and the amount of cobalt AEO-7 phthalocyanine is 0.01, 0.012g.
6. The method for catalytic desulfurization of cobalt AEO-7 phthalocyanine according to claim 1, wherein in the step (3), in the process of catalytic removal of thiophene by using cobalt AEO-7 phthalocyanine as a catalyst, the oxidant is oxygen in catalytically activated air, the desulfurization time is 3h, and the degradation rate is 90% or more.
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