CN106083867A - The preparation method of a kind of modified metal porphyrin and the application of catalytic oxidation desulfurization thereof - Google Patents

The preparation method of a kind of modified metal porphyrin and the application of catalytic oxidation desulfurization thereof Download PDF

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CN106083867A
CN106083867A CN201610563055.2A CN201610563055A CN106083867A CN 106083867 A CN106083867 A CN 106083867A CN 201610563055 A CN201610563055 A CN 201610563055A CN 106083867 A CN106083867 A CN 106083867A
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solution
modified metal
metal porphyrin
fuel oil
metalloporphyrin
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CN106083867B (en
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王建龙
赵日杰
李开喜
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
    • 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
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The preparation method of a kind of modified metal porphyrin is with metalloporphyrin as raw material, adds in dichloromethane, fully dissolves, be designated as solution 1, be dissolved in deionized water by displacer, be designated as solution 2；Solution 1 and solution 2 are mixed, stirs 10 ~ 30 hours at a temperature of 10 ~ 50 DEG C；After reaction terminates, solution is layered, and by upper and lower solution separating, and lower floor's solution carries out rotation steaming, i.e. obtains modified metal porphyrin.The present invention has simple to operate, the advantage being effectively increased the catalysis activity of metalloporphyrin.

Description

The preparation method of a kind of modified metal porphyrin and the application of catalytic oxidation desulfurization thereof
Technical field
The present invention relates to a kind of method of modified metal porphyrin and for the method being catalyzed oxidation fuel desulfuration.
Background technology
The SOx that in fuel oil, the burning of sulfur-containing compound generates causes the most serious atmosphere polluting problem.Meanwhile, SOx Also can acid etching automobile engine, make the catalyst poisoning in exhaust catalytic converter.Being directed to this, it is relevant that countries in the world are put into effect Sulfur content in Fuel Oil content has also been done concrete standard by policy, it is stipulated that sulfur content more and more lower.Now it is commercially used for fuel oil The method of desulfurization is mainly hydrodesulfurization, but for the sulfur-containing compound of aromatics, especially dibenzothiophenes and derivative The hydrogenation and removing of thing, needs very harsh condition, the operating cost of the great number brought.In consideration of it, some new sulfur methods As abstraction desulfurization, absorption desulfurization, oxidation sweetening, alkylating desulfurization, biological desulphurization etc. arise at the historic moment, deep for realizing under temperate condition Degree desulfurization provides new thinking.
Metal porphyrins is a kind of important bionic catalyst, is widely used in various catalytic oxidation, specially Profit CN101301627B, with metalloporphyrin as catalyst, has carried out sulfur oxide compound at high temperature and high pressure, the sulfide after oxidation Still exist in oil phase.Patent CN104277870A, with metalloporphyrin or phthalocyanine as catalyst, carries out photochemical catalytic oxidation, by C S bond fission, thus carry out desulfurization.Patent CN105419853A is with metalloporphyrin as catalyst, and ionic liquid is extractant, peroxide Changing hydrogen is that oxidant carries out extracting catalytic oxidation desulfurization.At present, the synthesis of metalloporphyrin is mainly synthesized by Alder method, Guo Bright cities etc. (patent CN103880851B, CN1238355C) optimize synthetic method, but the metalloporphyrin obtained by synthesis Axial ligand generally is chlorine.The catalysis activity of monokaryon iron porphyrin is had a significant impact by axial ligand, causes some metalloporphyrin Catalysis activity relatively low.
Summary of the invention:
It is an object of the invention to provide a kind of preparation method being catalyzed the high a kind of modified metal porphyrin of activity and catalysis thereof The application of oxidation sweetening.
The preparation method of modified metal porphyrin of the present invention, comprises the steps:
(1) with metalloporphyrin as raw material, add in dichloromethane, fully dissolve, be designated as solution 1；
(2) displacer is dissolved in deionized water, is designated as solution 2；
(3) solution 1 and solution 2 are mixed, stir 10～30 hours at a temperature of 10～50 DEG C；React solution after terminating Layering, by upper and lower solution separating, and carries out rotation steaming, i.e. obtains modified metal porphyrin lower floor's solution.
Wherein: the concentration of solution 1 is 0.1～3wt%, the concentration of solution 2 is 1～3wt%；Metalloporphyrin and displacer Molar fraction is than for 1:1～5.
Described displacer is ammonium tetrafluoroborate, ammonium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoro phosphate, potassium tetrafluoroborate Or the one in hexafluoro potassium borate.
Modified metal porphyrin application prepared by the present invention comprises the steps.
The mixing of modified metal porphyrin, ionic liquid and fuel oil is added in reactor, adds hydrogen peroxide, 25～60 Stirring, reacting by heating 1～6h at DEG C.
Wherein ionic liquid is 0.1～1:1 with the long-pending body ratio of fuel oil, and in fuel oil, total sulfur content and modified metal porphyrin rubs Your ratio is 40～220:1, and hydrogen peroxide is 1～5:1 with the mol ratio of total sulfur content in fuel oil.
Above-mentioned modified metal porphyrin used is one or more mixture in modified metal porphyrin prepared by the present invention.
Above-mentioned ionic liquid used is 1 butyl 3 Methylimidazole. hexafluorophosphate, 1 butyl 3 Methylimidazole. tetrafluoro boron One or both mixture in hydrochlorate.
The present invention rear metalloporphyrin structure before modified is as follows.
Wherein: R1=R2=R4=R5 is hydrogen, R3 is hydrogen, halogen, nitro, methyl, alkoxyl, hydroxyl, carboxyl；M is Fe, Co,Ni；L is BF4 -, PF6 -。
Advantages of the present invention:
1, the present invention is simple to operate, mild condition, and energy consumption is relatively low.
2, the most recyclable recycling of solvent for use of the present invention, it is to avoid the environmental problem that organic solvent causes.
3, the present invention effectively raises the catalysis activity of metalloporphyrin, and applies it to fuel desulfuration, desulfurized effect It is better than unmodified metalloporphyrin.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but protection scope of the present invention is not limited to implement The scope that example represents.
In following instance, analysis method used is GB/T380 88 oil product sulphur content determination method, and desulfurization degree=1 is (de- Sulphur content of fuel oil/raw oil sulfur content after sulfur).Dibenzothiophenes is dissolved in positive flow silane and prepares fuel oil, fuel oil total sulfur content It is 500 μ g/ml.
Embodiment 1
Metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) is dissolved in dichloromethane (0.1wt%), as solution 1, the ammonium tetrafluoroborate of 2 times of metalloporphyrin moles is dissolved in deionized water simultaneously (1wt%), as solution 2, solution 1 is added in solution 2, stir 30 hours at 20 DEG C, with separatory funnel isolated lower floor Solution, available modified metal porphyrin (formula 2, M=Fe, L=BF are steamed in rotation further4 ‐, R1=R2=R3=R4=R5=H), Yield 89%.
Embodiment 2
Metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) is dissolved in dichloromethane (3wt%) As solution 1, the sodium hexafluoro phosphate of 3 times of moles is dissolved in deionized water simultaneously (3wt%) as solution 2, by solution 1 Adding in solution 2, stir 10 hours at 10 DEG C, with separatory funnel isolated lower floor solution, available modification is steamed in rotation further Metalloporphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), yield 85%.
Embodiment 3
Metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) is dissolved in dichloromethane (0.2wt%) as solution 1, the ammonium hexafluorophosphate of 5 times of moles is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 20 hours at 25 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), yield 98%.
Embodiment 4
By metalloporphyrin (formula 1, M=Co, R1=R2=R4=R5=H, R3=NO3) be dissolved in dichloromethane (0.2wt%) as solution 1, the Potassium Hexafluorophosphate of equimolar amounts is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir about 10 hours at 50 DEG C, with separatory funnel isolated lower floor solution, revolve steaming further Available modified metal porphyrin (formula 2, M=Co, L=PF6 ‐, R1=R2=R4=R5=H, R3=NO3), yield 81%.
Embodiment 5
By metalloporphyrin (formula 1, M=Ni, R1=R2=R4=R5=H, R3=CH3) be dissolved in dichloromethane (0.2wt%) as solution 1, the Potassium Hexafluorophosphate of equimolar amounts is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 20 hours at 25 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Co, L=PF6 ‐, R1=R2=R4=R5=H, R3=CH3), yield 82%.
Embodiment 6
By metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=OCH3) be dissolved in dichloromethane (0.3wt%) as solution 1, the sodium tetrafluoroborate of 2 times of moles is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 20 hours at 25 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Fe, L=BF4 ‐, R1=R2=R4=R5=H, R3=OCH3), yield 89%.
Embodiment 7
Metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=Cl) is dissolved in dichloromethane (0.3wt%) as solution 1, the sodium tetrafluoroborate of 2 times of moles is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 30 hours at 25 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Fe, L=BF4 ‐, R1=R2=R4=R5=H, R3=Cl), yield 89%.
Embodiment 8
Metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=OH) is dissolved in dichloromethane (0.5wt%) as solution 1, the Potassium Hexafluorophosphate of 2 times of moles is dissolved in deionized water (1wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 30 hours at 20 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R4=R5=H, R3=OH), yield 88%.
Embodiment 9
Metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=COOH) is dissolved in dichloromethane (0.8wt%) as solution 1, the Potassium Hexafluorophosphate of 3 times of moles is dissolved in deionized water (2wt%) as solution simultaneously 2, solution 1 is added in solution 2, stir 30 hours at 25 DEG C, with separatory funnel isolated lower floor solution, rotation steaming can further Obtain modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R4=R5=H, R3=COOH), yield 94%.
Embodiment 10
By 0.5mL1 butyl 3 Methylimidazole. hexafluorophosphate, 5mL fuel oil, sulfur content and catalyst mole in fuel oil Ratio is 200:1, and catalyst is modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), add Volume is in the round-bottomed flask of 50mL, and adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 1:1.Magnetic is opened after sealing Power stirring and oil bath are heated to 60 DEG C, react 6h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 71%, and not Modified metal porphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) desulfurization degree under the same conditions is 50%.
Embodiment 11
By 2mL1 butyl 3 Methylimidazole. hexafluorophosphate, 5mL fuel oil, sulfur content and catalyst mole ratio in fuel oil For 100:1, catalyst is modified metalloporphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), add Volume is in the round-bottomed flask of 50mL, and adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 3:1.Magnetic is opened after sealing Power stirring and oil bath are heated to 60 DEG C, react 5h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 99.8%, and Unmodified metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) desulfurization degree under the same conditions is 93%.
Embodiment 12
By 5mL1 butyl 3 Methylimidazole. hexafluorophosphate, 5mL fuel oil, sulfur content and catalyst mole ratio in fuel oil For 40:1, catalyst is modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), add and hold Amassing as in the round-bottomed flask of 50mL, adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 1:1.Magnetic force is opened after sealing Stirring and oil bath are heated to 25 DEG C, react 1h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 85%, and does not changes Property metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) desulfurization degree under the same conditions is 61%.
Embodiment 13
By 2mL1 butyl 3 methyl imidazolium tetrafluoroborate, 5mL fuel oil, sulfur content and catalyst mole ratio in fuel oil For 40:1, catalyst is modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R3=R4=R5=H), add and hold Amassing as in the round-bottomed flask of 50mL, adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 3:1.Magnetic force is opened after sealing Stirring and oil bath are heated to 60 DEG C, react 4h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 74%, and does not changes Property metalloporphyrin (formula 1, M=Fe, R1=R2=R3=R4=R5=H) desulfurization degree under the same conditions is 38%.
Embodiment 13
By 2mL1 butyl 3 Methylimidazole. hexafluorophosphate, 5mL fuel oil, sulfur content and catalyst mole ratio in fuel oil For 40:1, catalyst is modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R4=R5=H, R3=Cl), add Volume is in the round-bottomed flask of 50mL, and adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 3:1.Magnetic is opened after sealing Power stirring and oil bath are heated to 60 DEG C, react 4h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 98%, and not Modified metal porphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=Cl) desulfurization degree under the same conditions is 78%.
Embodiment 14
By 2mL1 butyl 3 Methylimidazole. hexafluorophosphate, 5mL fuel oil, sulfur content and catalyst mole ratio in fuel oil For 40:1, catalyst is modified metal porphyrin (formula 2, M=Fe, L=PF6 ‐, R1=R2=R4=R5=H, R3=NO3), add Entering in the round-bottomed flask that volume is 50mL, adding with sulfur content mol ratio in fuel oil is the hydrogen peroxide of 2:1.Open after sealing Magnetic agitation and oil bath are heated to 60 DEG C, react 4h.Being separated with ionic liquid by fuel oil after reaction, desulfurization degree is 93%, and Unmodified metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5=H, R3=Cl) desulfurization degree under the same conditions is 85%.
Embodiment 15
By 1mL1 butyl 3 Methylimidazole. hexafluorophosphate, 1mL1 butyl 3 methyl imidazolium tetrafluoroborate, 5mL fires Oil, in fuel oil, sulfur content and catalyst mole are than for 40:1, and catalyst is modified metal porphyrin (formula 2, M=Fe, L= PF6 ‐, R1=R2=R4=R5=H, R3=NO3), add in the round-bottomed flask that volume is 50mL, add and contain with sulfur in fuel oil Amount mol ratio is the hydrogen peroxide of 2:1.Open magnetic agitation after sealing and oil bath is heated to 60 DEG C, react 4h.Will combustion after reaction Oil is separated with ionic liquid, and desulfurization degree is 83%, and unmodified metalloporphyrin (formula 1, M=Fe, R1=R2=R4=R5 =H, R3=Cl) under the same conditions desulfurization degree be 65%.

Claims (6)

1. the preparation method of a modified metal porphyrin, it is characterised in that comprise the steps:
(1) with metalloporphyrin as raw material, add in dichloromethane, fully dissolve, be designated as solution 1；
(2) displacer is dissolved in deionized water, is designated as solution 2；
(3) solution 1 and solution 2 are mixed, stir 10～30 hours at a temperature of 10～50 DEG C；After reaction terminates, solution divides Layer, by upper and lower solution separating, and carries out rotation steaming, i.e. obtains modified metal porphyrin lower floor's solution；
Wherein: the concentration of solution 1 is 0.1～3wt%, the concentration of solution 2 is 1～3wt%；Metalloporphyrin and displacer mole Score ratio is 1:1～5.
The preparation method of a kind of modified metal porphyrin the most as claimed in claim 1, it is characterised in that described displacer is four One in ammonium fluoroborate, ammonium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoro phosphate, potassium tetrafluoroborate or hexafluoro potassium borate.
The preparation method of a kind of modified metal porphyrin the most as claimed in claim 1, it is characterised in that metalloporphyrin structural formula is such as Under:
Wherein: R1=R2=R4=R5 is hydrogen, R3 is hydrogen, halogen, nitro, methyl, alkoxyl, hydroxyl, carboxyl；M is Fe, Co, Ni；L is BF4 -, PF6 -。
4. the preparation method of a kind of modified metal porphyrin as described in any one of claim 13, it is characterised in that modified metal Porphyrin structure formula is as follows:
Wherein: R1=R2=R4=R5 is hydrogen, R3 is hydrogen, halogen, nitro, methyl, alkoxyl, hydroxyl, carboxyl；M is Fe, Co, Ni；L is BF4 -, PF6 -。
5. the application of the modified metal porphyrin as described in any one of claim 15, it is characterised in that comprise the steps:
The mixing of modified metal porphyrin, ionic liquid and fuel oil is added in reactor, adds hydrogen peroxide, at 25～60 DEG C Stirring, reacting by heating 1～6h；
Wherein ionic liquid is 0.1～1:1 with the long-pending body ratio of fuel oil, total sulfur content and the mol ratio of modified metal porphyrin in fuel oil Being 40～220:1, hydrogen peroxide is 1～5:1 with the mol ratio of total sulfur content in fuel oil.
6. the application of modified metal porphyrin as claimed in claim 5, it is characterised in that ionic liquid used is 1 butyl 3 first One or both mixture in base limidazolium hexafluorophosphate, 1 butyl 3 methyl imidazolium tetrafluoroborate.
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