CN101285003A - Applications of molybdenum based metal Carbonitride mesenchymal alloy for sulfur removal in fuel - Google Patents
Applications of molybdenum based metal Carbonitride mesenchymal alloy for sulfur removal in fuel Download PDFInfo
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- CN101285003A CN101285003A CNA2008101238257A CN200810123825A CN101285003A CN 101285003 A CN101285003 A CN 101285003A CN A2008101238257 A CNA2008101238257 A CN A2008101238257A CN 200810123825 A CN200810123825 A CN 200810123825A CN 101285003 A CN101285003 A CN 101285003A
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Abstract
The invention relates to an application of alloy compounds filling between transition states of molybdenum based nitrogen and carbon in deep desulfurization of fuel oil. Alloy adsorbing materials filling between the molybdenum based nitrogen and the carbon can be MoNxCy, M1MoNxCy or M1M2MoNxCy, wherein M1 and M2 can be transition metals except Mo. Under the normal pressure and at a temperature of between 0 and 100 DEG C, the fuel oil passes through an adsorbing bed layer of alloy filling between the molybdenum based nitrogen and the carbon at a certain air speed to remove sulfides contained in the fuel oil in high efficiency by selective chemical adsorption, thereby an ultra-clean fuel oil is prepared, the sulfur content of which is below 15ppm. The adsorptive desulfurization process applied in the invention can be operated under conditions of normal pressure, normal temperature or near normal temperature; thereby equipment investment and operating costs are greatly lowered.
Description
Technical field
The invention belongs to oil fuel refining field.Relate to novel an of class and fill the application of alloy cpd aspect the desulfurization of fuel oil, the application of a class molybdenum based metal Carbonitride mesenchymal alloy aspect the oil fuel deep desulfuration of more specifically saying so.
Background technology
With the raising of environmental requirement, more and more stricter to the restriction of sulphur content in the oil fuel.Environmental Protection Agency (US EPA) specified requirement sulfur in gasoline content is controlled at below the 30ppm, and the derv fuel oil sulphur content is controlled at below the 15ppm.Also there are similar regulation in European Union and Japan.
Concerning refinery,, be still the comparatively scheme of reality by improving hydrorefined effect for reaching the requirement of new environmental regulation.So each major company and research institution put forth effort on the new shortening technology of exploitation.As Akzo, Nobel, Criterion, Haldor-Topsoe, IFP, ExxonMobil, Sinopec research institute, Fushun research institute and Dalian materialization etc. developed new deep hydrofinishing catalyzer in succession (base type be: NiMoS/Al
2O
3, CoMoS/Al
2O
3, CoMoS/MCM-41, NiWS/Al
2O
3, Ni2P/SiO
2, γ-Mo
2N).For seeking deep refining technology cheaply, Phillips has developed the oil company so-called S-Sorb pyrochemistry absorption low-voltage hydrogenation process.Deep hydrogenation consumes a large amount of H on the one hand
2And energy, on the other hand because the restriction of chemical equilibrium is difficult to reach new standard.Especially to diesel oil, because sulfide wherein mainly is to be difficult to many ring derivatives such as activatory thionaphthene, dibenzothiophene.
Except that hydrofinishing process, non-hydrogenation technology is not because consume H
2, invest little and come into one's own.The B﹠amp of the U.S.; Sorbent material is made with modified aluminas by V company, developed the refining with adsorbents technology (US 5730860) that is called Irvad, but adsorption efficiency is lower.U.S. Petro Star company, Sulph company and Japan petroleum energy company all develop desulfurization by oxidation and extraction technology in succession, but extraction agent consumption is big, cost is high.British Petroleum Company p.l.c. (BP) improves the organic sulfide boiling point with alkylated reaction, reaches the purpose of desulfurization subsequently by distillation, and operation efficiency is low, and the more difficult further processing of alkylating sulfide.Chinese patent (CN1148436C) has also proposed the refining fuel oil technology of polynary heteropoly acid catalysis oxidation-extraction method, but running cost height, extraction phase are difficult.
Above-mentioned desulfurization technology is reversing process mostly, is subjected to chemical equilibrium or the restriction that balances each other, and is difficult to the super clean fuel of preparation sulphur content below 30ppm.
Summary of the invention
The objective of the invention is to adopt novel catalytic adsorption material, under the demulcent condition, the sulphur in the oil product is adsorbed, prepare super clean fuel, thereby exploitation is efficient, less energy-consumption, super clean fuel (being that sulphur content is below 15ppm) technology of preparing cheaply.
The object of the present invention is achieved like this: adopt molybdenum based metal Carbonitride mesenchymal alloy as sorbing material, at normal pressure with oil fuel with the adsorption bed of certain air speed by molybdenum based metal Carbonitride mesenchymal alloy, adsorb the sulfide of efficiently removing in the oil fuel through selective chemical, thus the following super clean fuel oil of preparation sulfur-bearing 15ppm.Monitor the sulphur content of refined oil with the gas chromatograph of band hydrogen flame fluorimetric detector (FPD).
The molybdenum based metal Carbonitride mesenchymal alloy that uses among the present invention can be MoN
xC
y, M
1MoN
xC
yOr M
1M
2MoN
xC
y(span of x, y is 0.01～1.0), wherein M
1, M
2Can be the transition metal except that Mo, that suitable be Cu, Ni, Co, Pt, Pd, Ru, Ag, Au, Zn, Cr, W, Fe etc.
The carrier that sorbing material adopted among the present invention can be γ-Al
2O
3, porous material such as MCM-41, H-Y, H-β.
Monometallic nitrogen carbide (MoN among the present invention
xC
y) the charge capacity of molybdenum can be 4%～30%, wherein sweetening effectiveness is preferably the charge capacity 12%～20% of molybdenum; Bimetal nitrogen carbide (M
1MoN
xC
y) or three metal nitrogen carbide (M
1M
2MoN
xC
y) in M1, M2 and the atomic ratio of Mo be M1 (M2): Mo=0.1～1: 1, (M1+M2): Mo=0.2～1.5: 1; M1: M2=0.3～1: 1.
The molybdenum based metal Carbonitride mesenchymal alloy that uses among the present invention records surface nitrogen element (N) content 0.02～0.4%, surface carbon element (C) content 0.2～1.5% after loading to carrier.
In the process of desulfurization of the present invention, the temperature of adsorption and enrichment is 0～100 ℃, and suitable temperature is 10～80 ℃.
The air speed that is adopted in the process of adsorption desulfurize of the present invention can be 1～10h
-1, that wherein more suitable is 1～7.5h
-1
Used oil fuel can be gasoline, kerosene or diesel oil among the present invention.
The present invention has following advantage:
(1) chemical action with highly selective of prepared molybdenum based metal Carbonitride mesenchymal alloy of the present invention and the sulfide in the fuel oil can prepare the super clean fuel of sulphur content below 15ppm easily.
(2) process for adsorption desulfuration that the present invention taked can be operated under normal pressure, normal temperature or the condition near normal temperature, reduces facility investment and running cost widely.
The specific examples mode
Embodiment 1:
Be that to fill alloy MoNxCy/ γ-Al2O3 between 12% monometallic nitrogen carbonization be sorbing material with the charge capacity of molybdenum, surface nitrogen element (N) content 0.136%, surface carbon element (C) content 0.484%.Commercially available No. 93 gasoline (sulphur content 138mg/L) air speed is 7.5h-1, and 50 ℃ are carried out adsorption desulfurize.Desulfurization the results are shown in Table 1.
Embodiment 2:
Change the charge capacity of molybdenum in the example 1 into 7%, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 1.
Embodiment 3:
Change the charge capacity of molybdenum in the example 1 into 4%, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 1.
Embodiment 4:
Change the charge capacity of molybdenum in the example 1 into 18%, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 1.
Embodiment 5:
Change the charge capacity of molybdenum in the example 1 into 20%, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 1.
Embodiment 6:
Change the charge capacity of molybdenum in the example 1 into 30%, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 1.
Table 1 molybdenum charge capacity is to the influence of monometallic nitrogen molybdenum carbide adsorption desulfurize
Embodiment 7:
Change the carrier of sorbing material in the example 1 into MCM-41, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 2.
Embodiment 8:
Change the carrier of sorbing material in the example 1 into H-Y, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 2.
Embodiment 9:
Change the carrier of sorbing material in the example 1 into H-β, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 2.
Table 2 kind of carrier is to the influence of monometallic nitrogen molybdenum carbide adsorption desulfurize
Embodiment 10:
Change air speed in the example 1 into 1h
-1, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 3.
Embodiment 11:
Change air speed in the example 1 into 3h
-1, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 3.
Embodiment 12:
Change air speed in the example 1 into 5h
-1, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 3.
Embodiment 13:
Change air speed in the example 1 into 10h
-1, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 3.
Table 3 air speed is to the influence of monometallic nitrogen molybdenum carbide adsorption desulfurize
Embodiment 14:
Change the temperature of adsorption desulfurize in the example 1 into 25 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Embodiment 15:
Change the temperature of adsorption desulfurize in the example 1 into 40 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Embodiment 16:
Change the temperature of adsorption desulfurize in the example 1 into 15 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Embodiment 17:
Change the temperature of adsorption desulfurize in the example 1 into 65 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Embodiment 18:
Change the temperature of adsorption desulfurize in the example 1 into 0 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Embodiment 19:
Change the temperature of adsorption desulfurize in the example 1 into 100 ℃, other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 4.
Table 4 adsorption temp is to the influence of monometallic nitrogen molybdenum carbide adsorption desulfurize
Embodiment 20:
Change monometallic nitrogen molybdenum carbide in the example 1 into the bimetal nitrogen carbide, second metal is Ni, and its charge capacity is 1/3 of a molybdenum, and other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 5.
Embodiment 21:
Change monometallic nitrogen molybdenum carbide in the example 1 into the bimetal nitrogen carbide, second metal is Co, and its charge capacity is 2/3 of a molybdenum, and other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 5.
Embodiment 22:
Change monometallic nitrogen molybdenum carbide in the example 1 into the bimetal nitrogen carbide, second metal is Cu, and its charge capacity is 3/3 of a molybdenum, and other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 5.
Embodiment 23:
Change monometallic nitrogen molybdenum carbide in the example 1 into the bimetal nitrogen carbide, second metal is Ni, and its charge capacity is 1/10 of a molybdenum, and other conditions are constant, carry out gasoline absorbing desulfurization.Desulfurization the results are shown in Table 5.
Table 5 second metal species and atomic ratio are to the influence of adsorption desulfurize
Embodiment 24～26
To fill alloy M between three metal nitrogen carbonizations
1M
2MoN
xC
y/ γ-Al
2O
3Be sorbing material, metal species and proportioning are listed in table 6, and other condition is with example 1, and gasoline absorbing desulfurization the results are shown in Table 6.
Fill alloy adsorption desulfurize result between table 6 three metal nitrogen carbonizations
Embodiment 27
Change gasoline in the example 25 into kerosene and carry out adsorption desulfurize, desulfurization the results are shown in Table 7.
Embodiment 28
Change gasoline in the example 25 into kerosene and carry out adsorption desulfurize, desulfurization the results are shown in Table 7.
The effect of the different oil product adsorption desulfurizes of table 7
Claims (4)
1. the application of molybdenum based metal Carbonitride mesenchymal alloy in fuel desulfuration, it is characterized in that adopting molybdenum based metal Carbonitride mesenchymal alloy as sorbing material, at normal pressure oil fuel is passed through the molybdenum based metal Carbonitride mesenchymal alloy adsorption bed with certain air speed, adsorb the sulfide of efficiently removing in the oil fuel through selective chemical, the following super clean fuel oil of preparation sulfur-bearing 15ppm; Described molybdenum based metal Carbonitride mesenchymal alloy is MoN
xC
y, M
1MoN
xC
yOr M
1M
2MoN
xC
y, wherein the span of x, y is 0.01～1.0, M
1, M
2Being the transition metal except that Mo, specifically is Cu, Ni, Co, Pt, Pd, Ru, Ag, Au, Zn, Cr, W, Fe;
The carrier that described sorbing material adopted is porous material γ-Al
2O
3, MCM-41, H-Y, H-β;
Fill alloy MoN between the carbonization of described monometallic nitrogen
xC
yThe charge capacity of molybdenum be 4%～30%; Fill alloy M between the carbonization of bimetal nitrogen
1MoN
xC
yOr three fill alloy M between the carbonization of metal nitrogen
1M
2MoN
xC
yIn M
1, M
2With the atomic ratio of Mo be M
1Or M
2: Mo=0.1～1: 1, (M
1+ M
2): Mo=0.2～1.5: 1; M
1: M
2=0.3～1: 1;
In the process of described adsorption desulfurize, the temperature of adsorption and enrichment is 0～100 ℃;
In the process of described adsorption desulfurize, the air speed that is adopted is 1～10h
-1
Described oil fuel is gasoline, kerosene or diesel oil.
2. the application of molybdenum based metal Carbonitride mesenchymal alloy according to claim 1 in fuel desulfuration, the charge capacity that it is characterized in that filling between the carbonization of described monometallic nitrogen the molybdenum of alloy MoNxCy is 12%～20%.
3. the application of molybdenum based metal Carbonitride mesenchymal alloy according to claim 1 in fuel desulfuration is characterized in that in the process of described desulfurization that the temperature of adsorption and enrichment is 10～80 ℃.
4. the application of molybdenum based metal Carbonitride mesenchymal alloy according to claim 1 in fuel desulfuration is characterized in that the air speed that is adopted is 1～7.5h-1 in the process of described adsorption desulfurize.
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|---|---|---|---|
| CN2008101238257A CN101285003B (en) | 2008-06-05 | 2008-06-05 | Applications of molybdenum based metal carbonitride mesenchymal alloy for sulfur removal in fuel |
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|---|---|---|---|
| CN2008101238257A CN101285003B (en) | 2008-06-05 | 2008-06-05 | Applications of molybdenum based metal carbonitride mesenchymal alloy for sulfur removal in fuel |
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|---|---|
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| CN101285003B CN101285003B (en) | 2012-05-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109794279A (en) * | 2019-02-22 | 2019-05-24 | 中国林业科学研究院林产化学工业研究所 | A kind of MoC/CN catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851206A (en) * | 1981-07-15 | 1989-07-25 | The Board Of Trustees Of The Leland Stanford Junior University, Stanford University | Methods and compostions involving high specific surface area carbides and nitrides |
| CN1179020C (en) * | 2001-08-16 | 2004-12-08 | 中国石油化工股份有限公司 | Gasolene desulfurizing method by adsorption |
-
2008
- 2008-06-05 CN CN2008101238257A patent/CN101285003B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109794279A (en) * | 2019-02-22 | 2019-05-24 | 中国林业科学研究院林产化学工业研究所 | A kind of MoC/CN catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
| CN109794279B (en) * | 2019-02-22 | 2022-04-05 | 中国林业科学研究院林产化学工业研究所 | MoC/CN catalyst, preparation method thereof and application thereof in oleic acid hydrodeoxygenation reaction |
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|---|---|
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