CN102373078A - Deep hydrodesulfurization method for diesel oil - Google Patents
Deep hydrodesulfurization method for diesel oil Download PDFInfo
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- CN102373078A CN102373078A CN2010102526742A CN201010252674A CN102373078A CN 102373078 A CN102373078 A CN 102373078A CN 2010102526742 A CN2010102526742 A CN 2010102526742A CN 201010252674 A CN201010252674 A CN 201010252674A CN 102373078 A CN102373078 A CN 102373078A
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000003921 oil Substances 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910002796 Si–Al Inorganic materials 0.000 claims abstract description 3
- YNDJWINAKRFTHX-UHFFFAOYSA-N [S].[W].[Ni].[Co] Chemical compound [S].[W].[Ni].[Co] YNDJWINAKRFTHX-UHFFFAOYSA-N 0.000 claims abstract description 3
- RAFNAMHEPCFDRC-UHFFFAOYSA-N [W].[Mo].[Co].[Ni] Chemical compound [W].[Mo].[Co].[Ni] RAFNAMHEPCFDRC-UHFFFAOYSA-N 0.000 claims abstract description 3
- UTOHPYCQNRYRAQ-UHFFFAOYSA-N cobalt;molybdenum;sulfanylidenenickel Chemical compound [Co].[Mo].[Ni]=S UTOHPYCQNRYRAQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 claims abstract description 3
- MJTGHOSEDLILBB-UHFFFAOYSA-N cobalt;sulfanylidenetungsten Chemical compound [Co].[W]=S MJTGHOSEDLILBB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 claims abstract description 3
- XOROUWAJDBBCRC-UHFFFAOYSA-N nickel;sulfanylidenetungsten Chemical compound [Ni].[W]=S XOROUWAJDBBCRC-UHFFFAOYSA-N 0.000 claims abstract description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 5
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000003209 petroleum derivative Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 description 20
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- -1 nickel aluminate Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for deep hydrodesulfurization of diesel oil; at the pressure of 6.0-11MPa, the temperature of 360 DEG and 370 ℃ and the space velocity of 1-1.5h-1And the hydrogen-oil ratio is 500-800/1, the FCC diesel oil is catalytically hydrotreated; the catalyst is supported nickel-molybdenum-sulfur, nickel-tungsten-sulfur, molybdenum sulfide, tungsten sulfide, cobalt-molybdenum-sulfur, cobalt-tungsten-sulfur, nickel-cobalt-molybdenum-sulfur, nickel-cobalt-tungsten-sulfur or cobalt-molybdenum-nickel-tungsten and Ni2A composite catalyst of P; the carrier being Al2O3、SiO2、SiO2-Al2O3An all-silicon molecular sieve or a Si-Al molecular sieve; the catalyst has small active component size, good dispersity and high activity, can almost completely convert dibenzothiophene and derivatives thereof which are most difficult to remove in petroleum distillate oil, and is suitable for the raw material pre-refining hydrodesulfurization in oil refining hydrofining and petrochemical production.
Description
Technical field
The present invention relates to a kind of method of deep hydrodesulfurizationof of diesel oil.
Background technology
Along with the require increasingly stringent of environment, the refining of petrol and diesel oil more and more come into one's own to motor vehicle emission.An important indicator estimating the petrol and diesel oil quality is a sulphur content.This is because the products of combustion of sulfocompound is SO
X, not only can cause acid rain, also can damage the ozone layer causes environmental pollution.In addition, the petrol and diesel oil of organic compounds containing sulfur not only quality is unstable, also can corrode relevant equipment.Therefore, the sulphur content that reduces oil product enjoys the concern of countries in the world, and is harsh more to the requirement of sulphur content.In various desulfurization approach, hydrogenating desulfurization (HDS) remains most widely used method, has has all researched and developed different types of catalyzer both at home and abroad.
In the hydrogenating desulfurization commercial catalyst, Akzo-Noble and Japanese Ketjen company have developed highly active Co-Mo series and the serial hydrogenation catalyst of Ni-Mo, like KF757 (Co-MO) and KF848 (Ni-Mo).KF757 is used for the distillate ultra-deep desulfurization can make sulphur content reach 50 μ gg
-1Denmark Topsoe company has developed TK-554, several kinds of deep desulfurization catalysts such as TK-573 and TK-574.The Criterion catalyst Co. has been developed Co-Mo catalyzer DC-2118 and Ni-Mo catalyzer DN-3110, and hydrodesulfurization activity is high, can be used for producing low-sulfur and ultra-low-sulphur diesel.It is that active ingredient FH-98 catalyzer and Co-Ni-W-Mo are the FH-DS catalyzer of active ingredient with Ni-W-Mo that the Ceng Ronghui etc. of domestic Fushun Petrochemical Research Institute (FRIPP) has developed, and has good hydrogenating desulfurization and hydrodenitrogenationactivity activity.The hydrogenating desulfurization of Ni-W component diesel oil single hop, the dearomatization catalyst RN-10B of the exploitation of Sinopec Beijing Research Institute of Petro-Chemical Engineering also have good performance.
See from the retrieval of patent and document; Active ingredient about the gasoline and diesel hydrogenation desulfurization catalyst mainly concentrates on Co-Mo and Ni-Mo catalyzer; And Preparation of catalysts technology is comparatively ripe, but its application in the oil fuel of preparation ultra-low sulfur is still less.In recent years, along with the raising day by day that environment protection characterizes, various countries require harsh further to the sulphur content of oil fuel, in order to reach this standard, adopts traditional Co-Mo and Ni-Mo catalyzer, and the loadings of catalyzer must increase and hydroprocessing condition harshness more.For this reason, the expert in the field attempts to tackle the development of hydrogenating desulfurization through developing new highly effective hydrogenation desulfurization catalyst with this.1990s, Oyama etc. have proposed metal phosphide, have because the hydrodesulfurization performance of Ni-Mo and Co-M like nickel two phosphorus catalysts.Subsequently, the metal phosphide catalyzer is treated as a kind of novel Hydrobon catalyst broad research.
At present, the metal phosphorizing nickel catalyzator generally adopts the temperature-programmed reduction method preparation, and this method need be carried out under comparatively high temps.Therefore, when adopting Al
2O
3During for carrier, in the process of high temperature reduction nickel ion, cause nickel aluminate to generate easily, make with Al
2O
3For the catalyst of phosphatizing nickel hydrodesulfurization activity of carrier lower.At present, efficiently the phosphide Hydrobon catalyst generally with SiO
2Be carrier, still, SiO
2The forming technique of carrier and surface acid amount thereof and acid matter have limited the industry of catalyzer and have promoted.The present invention is directed to the characteristics of above-mentioned phosphide, develop one to be easy to the Al of moulding
2O
3With molecular sieve be carrier, at first at the metallic sulfide of carrier surface load high dispersive, utilize the characteristics of sulfide self, the metal phosphorizing nickel deposition in sulfide surface, can either be overcome the generation of nickel aluminate, can utilize the superelevation hydrodesulfurization performance of nickel phosphide again.
Summary of the invention
The method that the purpose of this invention is to provide a kind of deep hydrodesulfurizationof of diesel oil, used catalyzer are that the 6-dimethyldibenzothiophene has the catalyzer of high reactivity desulfurization to thiophene, thionaphthene, 4.
The method of deep hydrodesulfurizationof of diesel oil of the present invention is at pressure 6.0-11MPa, and temperature 360-370 ℃, air speed are 1-1.5h
-1With hydrogen-oil ratio is to be 12500 μ g/g to sulphur content under the condition of 500-800/1, and nitrogen content is 1200 μ g/g, and density is the FCC diesel oil catalytic hydroprocessing of 0.911g/ml.
Catalyzer is load-type nickel molybdenum sulphur, nickel tungsten sulphur, moly-sulfide, tungsten sulfide, cobalt molybdenum sulphur, cobalt tungsten sulphur, nickel cobalt molybdenum sulphur, nickel cobalt tungsten sulphur or cobalt molybdenum nickel tungsten and Ni
2The composite catalyst of P.Catalyzer contains NiMo, NiW, Mo, W, CoMo, NiMo, NiMoW, CoMoW metal component.
Catalyzer is with resistant to elevated temperatures inorganic porous oxide material, like Al
2O
3, SiO
2, SiO
2-Al
2O
3, total silicon molecular sieve or Si-Al molecular sieve be carrier; Element or its compound with group vib and VIII family are active ingredient, like Co, Mo, Ni, W monomer or NiMo, NiW, CoMo, CoW, NiMoW, CoMoW composition metal.Catalyzer is pinched through overmulling, extrusion, drying, the preparation of the method for roasting is trifolium-shaped, after processing with carrier incipient impregnation ortho phosphorous acid nickel and contain metal-salts such as Co, Ni, Mo, W.Obtain containing Ni through calcination process
2The catalyzer of P thing phase, 200～400 ℃ of treatment temps, the treatment time is 2～6h, the mass loading amount of nickel phosphide is 5～30%.To contain Ni then
2The catalyzer of P thing phase vulcanizes, and the pre-curing temperature of catalyzer is 250～450 ℃, and the prevulcanized time is 3h.The charge capacity of nickel phosphide is 5～30w%, and catalyzer contains Co, Ni, Mo, W metal component simultaneously, and metal component accounts for 5～50% of catalyst weight.
The method of deep hydrodesulfurizationof of diesel oil of the present invention is to make catalyzer through use metal phosphorus sulphur compound, makes catalyst surface generate metal phosphorus sulfur bond, and then improves the hydrodesulfurization activity of catalyzer.It is little that prepared catalyzer has an active ingredient yardstick, good dispersion degree, and catalyst activity is high, can the most difficult dibenzothiophene that removes and verivate thereof in the fraction oil of petroleum almost all be transformed.Be fit to be applied to make raw material pre-refining Hydrobon catalyst in oil refining Hydrobon catalyst and the petrochemical complex production.
Embodiment
Embodiment 1
With industrial Al (OH)
3Be raw material, warp mixes and pinches, extrusion, dries 6h down at 120 ℃, through 350～550 ℃ of roasting 4h, makes support of the catalyst again.The mixing solutions of ortho phosphorous acid nickel and nickelous nitrate, ammonium molybdate, ammonium metawolframate impregnated on the support of the catalyst,, contain Ni through what 350～550 ℃ of roastings obtained again 80～250 ℃ of oven dry down
2The precursor of the catalyzer of the active phase of P.The logical H of catalyzer precursor with gained
2S vulcanizes, and obtains catalyst n i
2P-NiMoWS/ γ-Al
2O
3, Ni in the catalyzer
2The weight percentage of P is 5%, and Ni, Mo and W metal account for catalyst weight per-cent 20%.
Embodiment 2
With industrial Al (OH)
3Be raw material, add the silicon sol of 10% weight ratio, warp mixes and pinches, extrusion, dries 6h down at 120 ℃, again through 350-550 ℃ of roasting 4h, makes support of the catalyst.The mixing solutions of ortho phosphorous acid nickel and nickelous nitrate, ammonium metawolframate impregnated on the support of the catalyst,, contain Ni through what 350～550 ℃ of roastings obtained again 80～250 ℃ of oven dry down
2The precursor of the catalyzer of the active phase of P.The logical H of catalyzer precursor with gained
2S vulcanizes, and obtains catalyst n i
2P-NiWS/ γ-Al
2O
3, Ni in the catalyzer
2The weight percentage of P is 5%, and Ni and W metal account for catalyst weight per-cent 30%.。
Embodiment 3
With industrial Al (OH)
3Be raw material, add the silicon sol that reaches of 10% weight ratio, warp mixes and pinches, extrusion, dries 6h down at 120 ℃, again through 350-550 ℃ of roasting 4h, makes support of the catalyst.The mixing solutions of ortho phosphorous acid nickel and nickelous nitrate, ammonium molybdate impregnated on the support of the catalyst,, contain Ni through what 350～550 ℃ of roastings obtained again 80～250 ℃ of oven dry down
2The precursor of the catalyzer of the active phase of P.The logical H of catalyzer precursor with gained
2S vulcanizes, and obtains catalyst n i
2P-NiMoS/ γ-Al
2O
3, Ni in the catalyzer
2The weight percentage of P is 5%, and Ni and Mo metal account for catalyst weight per-cent 30%.
Embodiment 4
With SiO
2Be carrier, the mixing solutions of ortho phosphorous acid nickel and nickelous nitrate, ammonium molybdate impregnated on the support of the catalyst,, contain Ni through what 350～550 ℃ of roastings obtained again 80～250 ℃ of oven dry down
2The precursor of the catalyzer of the active phase of P.The logical H of catalyzer precursor with gained
2S vulcanizes, and obtains catalyst n i
2P-NiMoS/SiO
2, Ni in the catalyzer
2The weight percentage of P is 30%, and Ni and Mo metal account for catalyst weight per-cent 5%.
Embodiment 5
With USY is carrier, and the mixing solutions of ortho phosphorous acid nickel and nickelous nitrate, ammonium metawolframate impregnated on the support of the catalyst, 80～250 ℃ of oven dry down, contains Ni through what 350～550 ℃ of roastings obtained again
2The precursor of the catalyzer of the active phase of P.The logical H of catalyzer precursor with gained
2S vulcanizes, and obtains catalyst n i
2P-NiWS/USY, Ni in the catalyzer
2The weight percentage of P is 30%, and Ni and W metal account for catalyst weight per-cent 5%.
Embodiment 6
With the prepared catalyzer of embodiment 1; On 200ml continuous hydrogenation reaction unit, be 12500 μ g/g to sulphur content; Nitrogen content is 1200 μ g/g, and density is that the FCC diesel oil of 0.911g/ml carries out hydrotreatment, and 8.0MPa, temperature are that 370 ℃, air speed are 1.0h in the pressure position
-1Under 800/1 hydrogen-oil ratio, reached desulfurization degree 99.2%, the good result of denitrification percent 98.8%.
Embodiment 7
With the prepared catalyzer of embodiment 1; On 100ml continuous hydrogenation reaction unit, be 5800 μ g/g to sulphur content; Nitrogen content is 760 μ g/g, and density is that the FCC diesel oil of 0.885g/ml carries out hydrotreatment, and 6.0MPa, temperature are that 360 ℃, air speed are 1.5h in the pressure position
-1Under 500/1 hydrogen-oil ratio, reached desulfurization degree 99.4%, denitrification percent 99.1%, cetane value raising value 9, diesel yield＞99.5%, the good result of arene engaging scraping rate 50%.
Embodiment 8
With the prepared catalyzer of embodiment 2; On 100ml continuous hydrogenation reaction unit, be 7100 μ g/g to sulphur content; Nitrogen content is 245 μ g/g, and density is that the straight-run diesel oil of 0.835g/ml carries out hydrotreatment, and 6.0MPa, temperature are that 355 ℃, air speed are 2.0h in the pressure position
-1Under 500/1 hydrogen-oil ratio, reached desulfurization degree 99.6%, the good result of denitrification percent 99.5%.
Embodiment 9
With the prepared catalyzer of embodiment 3; On 100ml continuous hydrogenation reaction unit, be 3300 μ g/g to sulphur content; Nitrogen content is 745 μ g/g, and density is that the FCC diesel oil of 0.890g/ml carries out hydrotreatment, and 6.5MPa, temperature are that 360 ℃, air speed are 1.5h in the pressure position
-1Under 500/1 hydrogen-oil ratio, reached desulfurization degree 99.5%, the good result of denitrification percent 99.2%.
Embodiment 10
With the prepared catalyzer of embodiment 4; On 100ml continuous hydrogenation reaction unit, be 1200 μ g/g to sulphur content; Nitrogen content is 635 μ g/g, and density is that the FCC diesel oil of 0.882g/ml carries out hydrotreatment, and 6.5MPa, temperature are that 360 ℃, air speed are 1.5h in the pressure position
-1Under 500/1 hydrogen-oil ratio, reached desulfurization degree 99.3%, the good result of denitrification percent 98.1%.
Embodiment 11
With the prepared catalyzer of embodiment 5; On 100ml continuous hydrogenation reaction unit, be 4500 μ g/g to sulphur content; Nitrogen content is 185 μ g/g, and density is that the straight-run diesel oil of 0.820g/ml carries out hydrotreatment, and 6.0MPa, temperature are that 350 ℃, air speed are 2.0h in the pressure position
-1Under 500/1 hydrogen-oil ratio, reached desulfurization degree 99.7%, the good result of denitrification percent 98.7%.
Claims (1)
1. the method for a deep hydrodesulfurizationof of diesel oil is characterized in that: at pressure 6.0-11MPa, temperature 360-370 ℃, air speed are 1-1.5h
-1With hydrogen-oil ratio be under the condition of 500-800/1, be 12500 μ g/g to sulphur content, nitrogen content is 1200 μ g/g, density is the FCC diesel oil catalytic hydroprocessing of 0.911g/ml;
Catalyzer is load-type nickel molybdenum sulphur, nickel tungsten sulphur, moly-sulfide, tungsten sulfide, cobalt molybdenum sulphur, cobalt tungsten sulphur, nickel cobalt molybdenum sulphur, nickel cobalt tungsten sulphur or cobalt molybdenum nickel tungsten and Ni
2The composite catalyst of P; Carrier is Al
2O
3, SiO
2, SiO
2-Al
2O
3, total silicon molecular sieve or Si-Al molecular sieve; Maturing temperature 200-400 ℃, the time is 2-6h, and the mass loading amount of nickel phosphide is 5～30%, and metal component accounts for 5～50% of catalyst weight, and surplus is a carrier; To contain Ni then
2The catalyzer of the active phase of P vulcanizes, and the pre-curing temperature of catalyzer is 200～500 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248983A (en) * | 2013-06-28 | 2014-12-31 | 中国石油天然气股份有限公司 | SiO (silicon dioxide)2-Al2O3Preparation method of composite carrier |
| CN106582742A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon hydrogenation saturation catalyst and preparation method thereof |
| CN106890660A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN111036276A (en) * | 2019-12-09 | 2020-04-21 | 西南石油大学 | Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof |
| CN116139873A (en) * | 2022-11-30 | 2023-05-23 | 中国石油大学(华东) | Preparation method of space-limited nickel-molybdenum diesel hydrogenation catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1293227A (en) * | 1999-10-13 | 2001-05-02 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
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| CN104248983A (en) * | 2013-06-28 | 2014-12-31 | 中国石油天然气股份有限公司 | SiO (silicon dioxide)2-Al2O3Preparation method of composite carrier |
| CN106582742A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon hydrogenation saturation catalyst and preparation method thereof |
| CN106582742B (en) * | 2015-10-15 | 2019-11-08 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon hydrocatalyst for saturating and preparation method thereof |
| CN106890660A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN111036276A (en) * | 2019-12-09 | 2020-04-21 | 西南石油大学 | Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof |
| CN111036276B (en) * | 2019-12-09 | 2022-02-01 | 西南石油大学 | Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof |
| CN116139873A (en) * | 2022-11-30 | 2023-05-23 | 中国石油大学(华东) | Preparation method of space-limited nickel-molybdenum diesel hydrogenation catalyst |
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| CN102373078B (en) | 2014-02-26 |
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