CN1791662A - Process and catalyst for removing arsenic and one or more other metal compounds from a hydrocarbon feedstock - Google Patents
Process and catalyst for removing arsenic and one or more other metal compounds from a hydrocarbon feedstock Download PDFInfo
- Publication number
- CN1791662A CN1791662A CN200480013366.7A CN200480013366A CN1791662A CN 1791662 A CN1791662 A CN 1791662A CN 200480013366 A CN200480013366 A CN 200480013366A CN 1791662 A CN1791662 A CN 1791662A
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- China
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- arsenic
- compound
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- raw material
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 57
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 6
- 150000002736 metal compounds Chemical class 0.000 title abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 8
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 7
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- -1 molybdate compound Chemical class 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052759 nickel Inorganic materials 0.000 abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000003079 shale oil Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+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 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention pertains to a process and catalyst for removing arsenic and one or more other metal compounds, e.g. silicon, vanadium and nickel, from a hydrocarbon feedstock. The catalyst comprises a molybdenum compound and a nickel compound on a carrier. The catalyst has a surface area of at least 200 m<2>/g. Next to contaminant removal, the catalyst is also suitable for hydrodesulphurisation, hydrodenitrogenation and/or hydrogenation.
Description
The present invention relates to a kind ofly from hydrocarbon raw material, remove the method for arsenic and one or more other metallic compounds and relate to a kind of wherein catalyst for application that is adapted at.Particularly relate to a kind of like this method of from hydrocarbon raw material, removing arsenic and one or more other metallic compounds, wherein raw material in the presence of hydrogen with inorganic carrier on contain nickel and molybdenum catalyzer contact.Also relate to a kind of special catalyst that is suitable for this method.
Generally speaking since other hydrocarbon fuel and the energy supply falls short of demand, shale oil and comprise that other heavy hydrocarbon fuel of the fuel that those are obtained by coal, tar sand etc. plays a part increasing in producing commercial hydrocarbon fuel.Usually, these raw materials contain various impurity, and they are used in these feed purifications so that these feedstock conversion become the poisoning of catalyst and the inactivation of useful product.Arsenic is bother most in these impurity a kind of, because it is very deleterious.Arsenic increases by 0.5% (weight) can make the catalytic activity of hydrotreating catalyst drop to below 5% of initial activity.In addition, the existence of arsenic on hydrotreating catalyst limited the utilization again of catalyzer, and may limit the processing selecting of using catalyzer.In distillate and VGO (vacuum gas oil) hydrotreatment, observe arseniasis, but, particularly after thermal conversion processes, in lighter raw material, also observe this point because some arsenic compound has low relatively boiling point.In fact, the existence of arsenic even may be in lighter raw material than in heavier raw material, causing more problem, because in lightweight material is used, use higher air speed usually.
Various reference have been described nickel-molybdenum catalyst in the application of removing arsenic from arsenical raw material.US 3804750 discloses and has a kind ofly contacted the method for removing arsenic from shale oil by shale oil with a kind of loaded catalyst, and described catalyzer contains 1-7% (weight), preferred 2-5% (weight) nickelous sulfide and 10-30% (weight), preferred 15-25% (weight) moly-sulfide on carrier.In an embodiment, by oxide compound, use the catalyzer that contains 3.2% (weight) Ni and 15% (weight) Mo.US 4046674 discloses the catalyzer that a kind of use contains one or more nickel components of 30-70% (weight) and one or more molybdenum components of 2-20% (weight) and refractory oxide combination, the method for removing arsenic from the mineral oil feed that contains 2ppmw arsenic at least.US 4501652 discloses a kind of hydrocarbon upgrading process, and wherein the spent catalyst with nickeliferous-arsenide is used for the hydrocarbon raw material upgrading.Nickel-molybdenum catalyst or nickel-tungsten catalyst are as the example of dearsenic catalyst.US 5421994 discloses a kind of method of removing mercury and arsenic from hydrocarbon raw material, wherein utilizes the arsenic recover materials be deposited on the metal that contains at least a metal that is selected from nickel, cobalt, iron, palladium and platinum and at least a chromium, molybdenum, tungsten and uranium on the carrier.In an embodiment, use reductive nickel/aluminium oxide catalyst.(the hydrofining of shale oil (the 4th part) dearsenification pre-treatment such as T.Hisamitsu, Sekiyu Gakkaishi, Vol.36, No.6, pp.479-484,1993) contain 12% (weight) Mo (18% (weight) MoO removing from the isolating vacuum gas oil fraction of shale oil to have compared the arsenic
3) and 3% (weight) Ni (3.8% (weight) NiO)/Al
2O
3Traditional hydrotreating catalyst with contain 5% (weight) Mo (7.5% (weight) MoO
3) and 33% (weight) Ni (42% (weight) NiO)/Al
2O
3Catalyzer.Japan's delay publication application form 60202190 discloses to use and has contained 0.5-20% (weight) NiO and 0.5-20% (weight) MoO
3Catalyzer from hydrocarbon raw material, remove arsenic.In an embodiment, use contains 5% (weight) NiO and 15% (weight) MoO
3Catalyzer.
From above-mentioned know find out that many documents recognize that catalyzer is by the problem of arseniasis.Should be pointed out that other metal that exists in arsenic not only but also the hydrocarbon raw material, the silicon, nickel or the vanadium that for example are exposed in such hydrocarbon raw material all may have detrimentally affect to metallic catalyzer.For example, be used for the noble metal catalyst of catalytic reforming by the silicon inactivation.In other words, only remove arsenic and may not be enough to prevent the metallic catalyst deactivation in downstream.Therefore, need a kind ofly can from hydrocarbon raw material, remove the catalyzer that arsenic removes one or more other metal components simultaneously.
Find that these problems can contain the nickel of specified amount and the catalyzer of molybdenum solves by use, described catalyzer also has at least 200 meters
2The surface-area of/gram.Therefore, the present invention relates to a kind of method of from hydrocarbon raw material, removing arsenic and one or more other metallic compounds, wherein containing at least 20ppb arsenic contacts with the catalyzer that contains molybdenum compound and nickel compound on carrier in the presence of hydrogen with the hydrocarbon raw material of other metallic compound of 0.3ppm at least, wherein by trioxide, the amount that molybdenum compound exists is 6-18% (weight), and by oxide compound, the amount that nickel compound exists is 6-20% (weight), and wherein the surface-area of catalyst composition is at least 200 meters
2/ gram.The catalyzer that is used for the inventive method can be removed arsenic and one or more other metallic compounds from hydrocarbon raw material simultaneously.Should be pointed out that on the kind of hydrocarbon raw material and decide that the type of other metallic compound and amount can change.Preferably, one of other metallic compound is a silicon.Catalyzer of the present invention can be enough to for example remove silicon with arsenic petroleum naphtha and the distillate from relative light-weight hydrocarbon raw material.Nickel and vanadium that catalyzer of the present invention also can exist in heavier hydrocarbon feeds are removed arsenic, reach the level of hope.
Catalyzer is removed from hydrocarbon raw material after the impurity, and common described catalyzer also is active in hydrogenating desulfurization and/or hydrodenitrification and/or hydrogenation.
In this manual, the term of use " % (weight) " refers to the total restatement by catalyzer, the weight percentage of certain compound in catalyzer.
As above-mentioned, by trioxide, the molybdenum content of catalyzer is 6-18% (weight), preferred 10-15% (weight).If the molybdenum content of catalyzer is too low, the gas generating amount of catalyzer (low molecular weight hydrocarbons, for example methane, ethane, propane and butane) is too high so.Add the molybdenum that surpasses the upper limit and make arsenic remove active decline, and make the decrease in efficiency of catalyzer.The nickel content of catalyzer is 6-20% (weight), preferred 8-15% (weight).Too low nickel content makes arsenic remove activity to drop to undesirable level.It is so low that the efficient of catalyzer and ability become, so that must regulate process variable in unacceptable mode economically, for example the air speed of the amount of catalyzer and raw material.The increase that should be pointed out that nickel content makes arsenic remove the capacity increase.But,, so the activity of catalyzer in hydrogenating desulfurization (HDS) and/or hydrodenitrification (HDN) had detrimentally affect if select to surpass the nickel content of the upper limit.
(BET) specific surface area of catalyzer of the present invention is at least 200 meters usually
2/ restrain, preferably be at least 225 meters
2/ restrain, more preferably be at least 250 meters
2/ gram.Described surface-area is at most 600 meters usually
2/ restrain, preferably be at most 500 meters
2/ restrain, more preferably be at most 400 meters
2/ gram.High relatively surface-area like this can improve the absorptive capacity of metallic compound, it is believed that in the carrier that absorbs the catalyzer use.Surface-area is lower than 200 meters
2/ gram catalyzer obtain metal remove ability particularly silicon remove the too low catalyzer of ability, do not have magnetism economically to cause described method.
Usually, catalyzer has at the most 15 nanometers, preferred 14 nanometers at the most, the more preferably mean pore sizes of 13 nanometers (MPD) at the most.MPD is at least 9 nanometers, preferably at least 9.5 nanometers, more preferably at least 10 nanometers usually.Mean pore sizes is defined as such aperture, and half of total pore volume is that the aperture surpasses the hole of MPD, and half of total pore volume is the hole of aperture less than MPD.The MPD of regulation has improved the accessibility that the metal that will remove enters catalyzer.Another advantage of selecting MPD to surpass 9 nanometers is that arsenic removes capacity and also improves.Should be pointed out that if select MPD less than 9 nanometers, so metal for example silicon, nickel or vanadium to remove capacity low, this is undesirable.On the other hand, if the MPD of catalyzer surpasses 15 nanometers, it obtains specific surface area usually less than 200 meters so
2The catalyzer of/gram, the activity that removes of described metal descends, so the efficient of catalyzer also descends.Another shortcoming that MPD surpasses 15 nanometers is that the activity of catalyzer in hydrogenating desulfurization, hydrodenitrification or hydrogenation descends.
The pore volume of catalyzer (Hg, 140 ° of contact angles) be generally at least 0.25 milliliter/gram, preferably at least 0.4 milliliter/gram, more preferably at least 0.5 milliliter/gram.Pore volume be generally 1.2 milliliters at the most/gram, preferably at the most 1.0 milliliters/gram, more preferably at the most 0.9 milliliter/gram.The macropore volume of catalyzer is less than 5%, preferably less than 2%, and described macropore volume is defined as the pore volume percentage ratio of diameter for the hole of at least 1000 dusts.
Carrier can comprise traditional oxide compound, and for example aluminum oxide, silicon oxide, silica-alumina, silica-alumina are dispersed in aluminum oxide wherein, aluminum oxide, magnesium oxide, zirconium white, boron oxide and titanium oxide of silica-coated and composition thereof.Usually, preferred vector comprise aluminum oxide, silica-alumina, silica-alumina be dispersed in wherein aluminum oxide or the aluminum oxide of silica-coated.Special preferred vector form by aluminum oxide basically or carrier basically by containing up to 25% (weight) other component, more preferably up to 10% (weight) other component, more preferably form up to the aluminum oxide of 5% (weight) other component, other component is preferably silicon oxide.Basically the carrier of being made up of aluminum oxide is particularly preferred.In this manual, term " basically by-... form " refer to that other component also can exist except that required component, but only in such finite quantity, so that they do not have injurious effects to the character of catalyzer.The aluminum oxide that exists in the carrier is preferably transition state of alumina, for example η, θ or gamma-alumina, and gamma-alumina is particularly preferred.For catalyzer, press P
2O
5Meter, it is preferred containing less than 2% (weight) phosphorus, being more preferably less than 1% (weight) phosphorus, being more preferably less than 0.5% (weight) phosphorus.
Other metal of catalyzer of the present invention is generally at least 3, preferably at least 4, most preferably at least 5 with the saturated capacity ratio of arsenic, usually at the most 20, preferably at the most 17 and most preferably at the most 15.Saturated capacity refers to the maximum that certain metal can be absorbed by catalyzer.Silicon is generally at least 3, preferably at least 4, most preferably at least 5 with the saturated capacity ratio of arsenic, and usually at the most 20, preferably at the most 17 and most preferably at the most 15.The nickel of catalyzer of the present invention and/or vanadium are generally at least 3, preferably at least 4, most preferably at least 5 with the saturated capacity ratio of arsenic, and usually at the most 20, preferably at the most 17 and most preferably at the most 15.
For particularly removing arsenic the petroleum naphtha type raw material, preferably remove arsenic with silicon from petroleum naphtha type raw material and distillate feedstock, the catalyzer in the above-mentioned most preferred range is considered to most preferred.
Catalyzer is preferably ball-type, pellet, microspheric form or extrusion type.The example that is fit to the extrusion type is open in the literature.Cylindrical particle (it may be hollow or not be hollow) and symmetric and asymmetric trilobal or quatrefoil particle are well suited for.
Catalyzer can prepare with this professional known method.
The raw material that is used for the inventive method contains 20ppb (per part per billion weight part) arsenic, particularly 0.02-2ppm arsenic at least.Also can contain other impurity.For example, may contain silicon.If like this, its amount is 0.5ppm, particularly 1-100ppm at least usually.Nickel and vanadium also may exist.If like this, its combined amount is 0.3ppm at least, preferred 100-2000ppm usually.These raw materials also contain sulfocompound and nitrogenous compound usually.Usually the amount of sulfocompound is 10ppm at least, and the amount of nitrogenous compound is 2ppm at least.Undersaturated compound for example alkene, diolefine and aromatic hydrocarbons also can exist.
A particularly preferred embodiment of the inventive method is to remove arsenic from arsenical petroleum naphtha type raw material, preferably removes arsenic with silicon.The arsenic content of the feed naphtha that is fit to is generally 20ppb at least, particularly 0.02-2ppm.Its silicone content is preferably 0.5ppm at least, particularly 1-100ppm.The amount of nickel and vanadium does not particularly have nickel or vanadium usually less than 10ppm in raw material.The initial boiling point of raw material is generally about 0-120 ℃, preferably about 30-90 ℃, and final boiling point is about 150-250 ℃, preferably about 160-220 ℃.In the method for this embodiment, catalyzer of the present invention is usually in hydrogenating desulfurization and hydrodenitrification and also be active in the saturation history of alkene and diolefine for example.
Another embodiment of the inventive method is to remove arsenic from distillate feedstock.The arsenic content of the distillate feedstock that is fit to is generally 20ppb at least, particularly 0.02-2ppm.They can contain silicon or can not contain silicon.If contain silicon, its amount is generally 0.5ppm at least, particularly 1-100ppm.The initial boiling point of raw material is generally about 80-260 ℃, preferably about 200-240 ℃, and final boiling point is about 230-390 ℃, preferably about 250-370 ℃.In the method for this embodiment, catalyzer of the present invention is usually in hydrogenating desulfurization and hydrodenitrification and also be active in the saturation history of alkene and diolefine for example.
The 3rd embodiment of the inventive method is to remove arsenic in oil fuel processing, usually with remove the combination of nickel and vanadium.The raw material that is used for the inventive method contains 20ppb arsenic at least, particularly 0.02-2ppm arsenic.The amount of nickel and vanadium is generally 0.3ppm, preferred 0.3-10ppm at least.Silicon can be contained or silicon can be do not contained.If contain silicon, its amount is generally 0.5ppm at least, particularly 1-100ppm.The initial boiling point of raw material is generally about 250-450 ℃, preferably about 280-375 ℃, and final boiling point is greater than 370 ℃.In the method for this embodiment, catalyzer of the present invention is usually in hydrogenating desulfurization and hydrodenitrification and also be active in the saturation history of aromatic hydrocarbons for example.
Described method is carried out under such condition usually, so that at least 50%, preferred at least 80%, more preferably at least 90%, more preferably at least 99% arsenic is removed from raw material.If contain silicon, at least 50%, preferred at least 80%, more preferably at least 90%, more preferably at least 98% silicon is removed from raw material so usually.If contain nickel and vanadium, at least 30%, preferably at least 60% from raw material, remove so usually.On the other hand, described method is carried out under such condition usually, thus at the most 50%, preferred at the most 20%, more preferably at the most 10%, more preferably 1% arsenic exists in the effluent of beds at the most.If contain silicon, so usually at the most 50%, preferred at the most 20%, more preferably at the most 10%, more preferably 2% silicon exists in the effluent of beds at the most.If contain nickel and vanadium, so usually at the most 70%, preferably 40% in the effluent of beds, exist at the most.
Method of the present invention is carried out in the operation of protection bed usually, prevents that just the downstream is influenced by arsenic to the catalyzer of arsenic sensitivity.Can in independent protection bed chamber or in the downstream of arsenic sensitive catalyst protection bed, carry out.Described method is carried out under hydrogen dividing potential drop 10-200 crust, preferred 30-150 crust and temperature 200-480 ℃, preferred 300-415 ℃ usually.Hydrogen/raw material ratio is generally 200-2000 mark and rises/liter, preferred 500-1000 mark rises/liter.The liquid hourly space velocity of measuring by the unit volume raw material flow rate of per unit volume catalyzer (LHSV) is generally 0.1-10 hour
-1, preferred 0.5-6 hour
-1
Embodiment
Following catalyzer is tested removing in the arsenic from arsenical raw material.Comparative catalyst 1 is contained 4% (weight) nickel (by oxide compound) and 12% (weight) molybdenum (by trioxide) on the alumina supporter, and the surface-area of catalyzer is about 250 meters
2/ gram, total pore volume (Hg, 140 ° of contact angles) is about 0.65-0.7 milliliter/gram, and MPD is about 11 nanometers.Catalyst A of the present invention is identical with comparative catalyst 1, and different is to contain 8% (weight) NiO.Catalyst B of the present invention is identical with comparative catalyst 1, and different is to contain 12% (weight) NiO.
These three kinds of catalyzer are tested removing in the arsenic from arsenical coking naphtha.After the test, find that these catalyzer have following arsenic and silicone content (normalizing is formed to live catalyst):
Table 1
The As content of spent catalyst (% (weight)) | The Si content of spent catalyst (% (weight)) | |
The comparative catalyst 1 | 1.03 | 0.95 |
Catalyst A | 1.66 | 1.04 |
Catalyst B | 2.00 | 1.08 |
Can know from last table 1 and to find out that compare with the comparative catalyst of containing than low nickel content, catalyzer of the present invention has higher dearsenification and silicon activity.
Claims (9)
1. method of from hydrocarbon raw material, removing arsenic and one or more other metallic compounds, wherein containing at least 20ppb arsenic contacts with the catalyzer that contains molybdenum compound and nickel compound on carrier in the presence of hydrogen with the hydrocarbon raw material of other metallic compound of 0.3ppm at least, wherein by trioxide, the amount that molybdenum compound exists is 6-18% (weight), and by oxide compound, the amount that nickel compound exists is 6-20% (weight), and wherein the surface-area of catalyst composition is at least 200 meters
2/ gram.
2. according to the process of claim 1 wherein by trioxide, the amount of molybdate compound is 10-15% (weight), and by oxide compound, the amount of nickel compound containing is 8-15% (weight).
3. according to the method for claim 1 or 2, wherein the MPD of catalyst composition is at least 9 nanometers, preferred 9-15 nanometer.
4. each method in requiring according to aforesaid right, wherein one of other metallic compound is a silicon.
5. each method in requiring according to aforesaid right, wherein raw material is a petroleum naphtha type raw material, its arsenic content is 20ppb (per 1,000,000,000/weight part) arsenic at least, preferred 0.02-2ppm arsenic, initial boiling point is about 0-120 ℃, preferably about 30-90 ℃, and final boiling point is about 150-250 ℃, preferably about 160-220 ℃.
6. according to the method for claim 5, wherein the silicone content of petroleum naphtha type raw material is 0.5ppm, particularly 1-100ppm at least.
7. each method in requiring according to aforesaid right, wherein said method rise at hydrogen dividing potential drop 10-200 crust, preferred 30-150 crust, temperature 200-480 ℃, preferred 300-415 ℃, hydrogen/raw material ratio 200-2000 mark/liter, preferred 500-1000 mark rises/liter and LHSV 0.1-10 hour
-1, preferred 0.5-3 hour
-1Under carry out.
8. hydrotreating catalyst that on carrier, contains molybdenum compound and nickel compound, wherein by trioxide, the amount of molybdenum compound is 6-18% (weight), and by oxide compound, the amount of nickel compound is 6-20% (weight), and wherein the surface-area of catalyzer is at least 200 meters
2/ gram.
9. hydrotreating catalyst according to Claim 8, wherein the MPD of catalyzer is at least 9 nanometers, preferred 9-15 nanometer.
Applications Claiming Priority (3)
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US47086403P | 2003-05-16 | 2003-05-16 | |
US60/470,864 | 2003-05-16 | ||
EP03076720.6 | 2003-06-03 |
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Publication Number | Publication Date |
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CN1791662A true CN1791662A (en) | 2006-06-21 |
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ID=34115296
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CN200480013366.7A Pending CN1791662A (en) | 2003-05-16 | 2004-05-06 | Process and catalyst for removing arsenic and one or more other metal compounds from a hydrocarbon feedstock |
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CN (1) | CN1791662A (en) |
WO (1) | WO2004101713A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101445748A (en) * | 2007-11-19 | 2009-06-03 | Ifp公司 | Two-step process for desulphurizing olefinic gasolines comprising arsenic |
CN106833731A (en) * | 2017-03-17 | 2017-06-13 | 钦州学院 | A kind of hydro-dearsenic method of naphtha |
CN106994351A (en) * | 2017-06-02 | 2017-08-01 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2478958A1 (en) | 2011-01-19 | 2012-07-25 | Euro Support Catalyst Group B.V. | Catalytically active material for hydration treatment of hydrocarbons |
EP2479242B1 (en) | 2011-01-19 | 2015-03-04 | Puralube Germany GmbH | Method for hydroprocessing of hydrocarbon compounds heavily contaminated with inorganic substances. |
RU2680386C1 (en) * | 2017-12-28 | 2019-02-20 | Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") | Method for hydrogeneration processing of raw materials |
RU2691067C1 (en) * | 2018-12-27 | 2019-06-10 | Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") | Hydrogenation refinement method of hydrocarbon material |
RU2691070C1 (en) * | 2018-12-27 | 2019-06-10 | Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") | Method of producing catalytically-sorption material and method of extracting arsenic in its presence |
RU2691072C1 (en) * | 2018-12-27 | 2019-06-10 | Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") | Method for combined extraction of arsenic and chlorine from oil distillates |
RU2737374C1 (en) * | 2019-10-03 | 2020-11-27 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Method for use of hydrodemetallization catalyst during hydrogenation processing of oil stock |
RU2761528C1 (en) * | 2021-01-27 | 2021-12-09 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Catalyst of a protective layer for reactors of hydrogenation processing of petroleum feedstock and a method for its production |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4102822A (en) * | 1976-07-26 | 1978-07-25 | Chevron Research Company | Hydrocarbon hydroconversion catalyst and the method for its preparation |
US4141820A (en) * | 1977-08-18 | 1979-02-27 | Chevron Research Company | Process for upgrading arsenic-containing oils |
US4601998A (en) * | 1983-08-17 | 1986-07-22 | Mobil Oil Corporation | Method and catalyst for removing contaminants from hydrocarbonaceous fluids using a copper-group via metal-alumina catalyst |
US4945079A (en) * | 1984-11-13 | 1990-07-31 | Aluminum Company Of America | Catalyst of nickel and molybdenum supported on alumina |
US5183561A (en) * | 1990-01-25 | 1993-02-02 | Mobil Oil Corp. | Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material |
-
2004
- 2004-05-06 CN CN200480013366.7A patent/CN1791662A/en active Pending
- 2004-05-06 WO PCT/EP2004/004943 patent/WO2004101713A1/en not_active Application Discontinuation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101445748A (en) * | 2007-11-19 | 2009-06-03 | Ifp公司 | Two-step process for desulphurizing olefinic gasolines comprising arsenic |
CN101445748B (en) * | 2007-11-19 | 2015-08-05 | Ifp公司 | For the two-step approach of the olefin gasolines desulfurization containing arsenic |
CN106833731A (en) * | 2017-03-17 | 2017-06-13 | 钦州学院 | A kind of hydro-dearsenic method of naphtha |
CN106994351A (en) * | 2017-06-02 | 2017-08-01 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
CN106994351B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
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WO2004101713A1 (en) | 2004-11-25 |
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