CN1668723A - A process for the hydroprocessing of heavy hydrocarbon feeds using at least two reactors - Google Patents
A process for the hydroprocessing of heavy hydrocarbon feeds using at least two reactors Download PDFInfo
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- CN1668723A CN1668723A CNA038165295A CN03816529A CN1668723A CN 1668723 A CN1668723 A CN 1668723A CN A038165295 A CNA038165295 A CN A038165295A CN 03816529 A CN03816529 A CN 03816529A CN 1668723 A CN1668723 A CN 1668723A
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- catalyst
- reactor
- temperature
- hydrotreating reactor
- asphaltene removal
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 239000011148 porous material Substances 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000010802 sludge Substances 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 206010037660 Pyrexia Diseases 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 229910052759 nickel Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000000243 solution Substances 0.000 description 7
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- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
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- 239000012535 impurity Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- 239000011574 phosphorus Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 229910052726 zirconium Inorganic materials 0.000 description 3
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007324 demetalation reaction Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical class CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
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- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention pertains to a process for hydroprocessing a heavy hydrocarbon feed using at least two reactors in which a heavy hydrocarbon feed is subjected sequentially to the steps of . hydroprocessing in a first hydroprocessing reactor, in which it is subjected sequentially to a hydrodemetallisation step, a hydrodesulfurisation step carried out at a temperature higher than that of said hydrodemetallisation step, and an asphaltene removal step carried out at a temperature higher than that of said hydrodesulfurisation step, . hydroprocessing in a second hydroprocessing reactor, in which it is subjected sequentially to a hydrodesulfurisation step and an asphaltene removal step, which latter is carried out at a temperature higher than that of said hydrodesulfurisation step. It has appeared that the use of an asphaltene removal catalyst in the hightemperature end of the two reactors, in combination with the specific reaction sequence, ensures that sludge formation is kept limited while efficient contaminant removal is obtained. This combination of features makes for an efficient and highly stable process.
Description
The present invention relates to a kind of method of using hydrotreating catalyst hydrotreatment of heavy hydrocarbon raw material.More specifically, the present invention relates to effectively reduce the hydroprocessing process of sulphur, metal, nitrogen and Kang Laxun carbon residue (CCR) in the heavy hydrocarbon feeds.
Heavy-hydrocarbon oil that produces in crude oil refining such as normal pressure resistates and vacuum residue comprise a large amount of various impurity such as sulphur, metal, nitrogen and Kang Laxun carbon residue.In recent years, increase day by day and use these heavy-hydrocarbon oil to remove impurity such as sulphur by hydroprocessing, obtain the product that is suitable as fuel oil and is fit to be converted into the light oil that economic worth is more arranged thus as raw material.
Treat in this raw material to comprise sulphur, Kang Laxun carbon residue (CCR), various metal by the impurity that the hydrotreatment operation is removed---more specifically be nickel and vanadium, nitrogen and bituminous matter.Various impurity wait that accurately the amount of removing is different because of raw material.
The whole bag of tricks of hydrotreatment of heavy hydrocarbon raw material has been described in prior art.
US 4,054, and 508 have described and a kind ofly may contain a large amount of bitum hydrocarbon ils, the demetalization of preferred residual fraction and three phase methods of hydrogenating desulfurization.First conversion zone contains and comprises the group vib metal that is carried on the alumina supporter, the macroporous catalyst of preferred Mo, this macroporous catalyst is that the hole of 100-200 has at least 60% pore volume for diameter, have pore volume for diameter greater than the hole of 500 , and preferred surface is long-pending up to 110m at least about 5%
2/ g.Second conversion zone comprises small catalyst, and this catalyzer contains hydrogenation component, is that the hole of 30-100 has at least 50%, preferred at least 60% pore volume for diameter, and surface-area is 150m at least
2/ g.The 3rd conversion zone contains the catalyzer identical with first conversion zone, but amount is lacked than it.Compare with small catalyst, macroporous catalyst has higher metal removal activity and lower desulphurizing activated.
US 4,431,525 disclose a kind of on tactic three kinds of catalyzer the method for the heavy hydrocarbon feeds of hydrotreatment asphaltenes, metal, nitrogen compound and sulphur compound.First kind of catalyzer is that catalyst for demetalation and the mean pore size that has are 12.5-35nm, and second kind of catalyzer is that Hydrobon catalyst and the mean pore size that has are 8-13nm.The third catalyzer (its purposes is not given) comprises Mo, Cr and Co, and the pore volume that has is that 0.4-0.8ml/g, surface-area are 150-300m
2/ g and mean pore size are 10-20nm.
US 5,744,025 disclose a kind of on tactic three kinds of catalyzer the method for the metallic heavy hydrocarbon feeds of hydrotreatment.First kind of catalyzer is catalyst for demetalation and is that the hole of 17-25nm has at least 40% pore volume for diameter, and surface-area is 100-160m
2/ g.Second kind of catalyzer can have demetalization and/or hydrogenating desulfurization and/or hydrodenitrification and/or Tuo Kanglaxun carbon residue activity, and it is that the hole of 3-17nm has at least 40% pore volume for diameter, and surface-area is 160-350m
2/ g.The third catalyzer is stated to be Hydrodemetalation catalyst, it comprises preferred negative and is stated from group vib and VIII family hydrogenation metal component on the aluminum oxide, it is that the hole of 17-25nm has at least 40%, preferred at least 60% pore volume for diameter, and surface-area is 100-160m
2/ g.
Japanese Patent Application Publication 2001-003066 discloses a kind of on tactic three kinds of catalyzer with different pore size distribution and then method of hydrotreatment heavy petrol in hydrodesulphurisatioreactors reactors.
Japanese Patent Application Publication 2000-351978 has described a kind of method of hydrotreatment of heavy hydrocarbon raw material, wherein the raw material order is carried out the step of the combination of hydrodemetallation (HDM), hydro-desulfurization and isomerization and hydrogenating desulfurization.
The Tuo Kanglaxun carbon residue is that a problem that runs in the heavy feed stock hydroprocessing of important goal is to form sludge therein.It is believed that the mechanism that forms sludge is as follows.Think that the Kang Laxun carbon residue comprises bituminous matter as its main ingredient.Bituminous matter is by having saturated hydrocarbon chain and the complicated polymer substance that constitutes of the nuclear of the fused polycycle aromatic hydrocarbons of the naphthalene system ring of bonding with it.They also contain sulphur, nitrogen and oxygen.They are insoluble in the normal hexane, but dissolve in disulphide and the benzene.In raw material, owing to have solvent composition, so bituminous matter exists with discrete form.Yet, if during hydroprocessing with bituminous matter and the too big degree hydrogenation of solvent composition, bituminous matter cohesion forms sludge (insoluble particle material) and sediment.
If sludge forms during hydroprocessing, then its sedimentation and in the various piece of a refining unit such as heat exchanger, reactor etc., depositing.If this phenomenon takes place, it can seriously disturb hydroprocessing, even the degree that may have to stop too early to operation.
In addition, the sludge of existence causes catalyst deactivation because of forming coke.For above-mentioned reasons, must raise the service temperature of this method to obtain identical product performance.This not only causes shortening cycling time, and causes energy wastage.
Although the method for describing in the above-mentioned reference is very good in carrying out the sulfuration of hydrodemetallation (HDM) and hydrogenation, but still has improved space.More specifically, need a kind of method that realize effectively removing dirt (hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification and Tuo Kanglaxun carbon residue), wherein Kang Laxun carbon residue and other dirt removes not follow and forms excessive sludge.
The method of the hydrotreatment of heavy hydrocarbon raw material of the present invention by at least two reactors of a kind of use are provided has solved this problem, in the method heavy hydrocarbon feeds is carried out following steps successively:
In first hydrotreating reactor, carry out hydrotreatment, wherein it is carried out hydrodemetallation (HDM) step, hydrodesulfurisationstep step and asphaltene removal step successively, wherein hydrodesulfurisationstep step is higher than in temperature under the temperature of described hydrodemetallation (HDM) step and carries out, asphaltene removal step is higher than in temperature under the temperature of described hydrodesulfurisationstep step carries out
Carry out hydrotreatment in second hydrotreating reactor, wherein it is carried out hydrodesulfurisationstep step and asphaltene removal step successively, back one step is higher than in temperature under the temperature of described hydrodesulfurisationstep step carries out.
The key of the inventive method is that raw material is handled in two reactors, and wherein asphaltene removal catalyst is present in the temperature end of two reactors.These characteristics of the present invention have just guaranteed that with combining of specific reaction sequence sludge forms the maintenance restriction, has realized the effective elimination of dirt simultaneously.This combination of each feature has obtained a kind of effective and high stability method.
Whole effluents can be imported second reactor from first reactor, but also can only liquid portion be imported second reactor from first reactor, or only the part of liquid portion be imported second reactor from first reactor.Preferably whole effluents or whole liquid efflunent are imported in another reactor.For back one situation, between reactor, will there be the gas/liquid stripping tower.To this, think that at present it is most preferred selecting whole liquid efflunents are imported in another reactor.Above-mentioned equally also being suitable for taken office the what situation of its reactor from second reactor.Can between two reactors intermediate reactor be set, these two reactors have asphaltene removal catalyst in its temperature end.In the case, above-mentionedly equally also be suitable for materials flow in the situation of any intermediate reactor.
But raw material autoreactor top is passed through reactor to the bottom or bottom the autoreactor to the top.From the top to the operation of bottom be modal.Catalyst sequences in this application provides along the raw material direction.
The reactor that uses in the inventive method is the reactor that is generally used in hydrotreatment and the olein refining.These reactors are adiabatic normally.Preferably on reactor, be provided for infeeding the device of hydrogen, to control inner temperature of reaction through quenching pipeline etc.The stripper plant that is used to remove hydrogen sulfide, ammonia etc. can be installed between reactor.
The different step of the inventive method is carried out under differing temps, and wherein the temperature of the hydrodesulfurisationstep step in first reactor is higher than the temperature of hydrodemetallation (HDM) step, and the temperature of asphaltene removal step is higher than the temperature of hydrodesulfurisationstep step.In second reactor, the temperature of asphaltene removal step is higher than the temperature of the hydrodesulfurisationstep step in second reactor again.In first reactor, the hydrodemetallation (HDM) step preferably 300-400 ℃, more preferably carry out under 350-380 ℃ the temperature.Hydrodesulfurisationstep step is subsequently carried out under the temperature that is higher than the hydrodemetallation (HDM) step.The hydrogenating desulfurization temperature is preferably 320-420 ℃, more preferably 360-410 ℃.In first reactor, asphaltene removal step is carried out being higher than under the temperature of hydrodesulfurisationstep step.This step is preferably carried out under the temperature of 350-450 ℃, more excellent 370-420 ℃.
Those temperature that provide in the correlation method in the hydrogenating desulfurization of carrying out in second reactor and non-essential other reactor and the preferred range of asphaltene removal step and top first reactor are identical.
The temperature of reaction that each conversion zone is provided is the average material temperature that is filled with on the entire reaction section of a certain type catalyst above.The temperature that hydrogenation takes off in the magnetic section is common than at least 2 ℃ of the temperature of reaction height in front-end hydrogenation demetalization section, is preferably up to few 4 ℃.Temperature of reaction in the asphaltene removal section is preferably up to few 4 ℃ usually than at least 2 ℃ of the temperature of reaction height in the front-end hydrogenation desulfurization section.This also is applicable to all reactors of the specific conversion zone that contains particular order.
Except that temperature of reaction, hydroprocessing condition does not have special restriction, can use conventional hydroprocessing condition.These conditions comprise that hydrogen partial pressure is generally 2-22MPa, preferred 10-20Mpa; The ratio of hydrogen and raw material is generally 300-1500Nl/l, preferred 600-1000Nl/l; And liquid hourly space velocity (LHSV) is generally 0.1-10h
-1, preferred 0.2-2.0h
-1
Fig. 1 is the schema of the inventive method.As shown in the drawing, hydrocarbon feed is at first infeeded in the reactor 1, and by the low-temperature zone 11 that contains Hydrodemetalation catalyst, the medium temperature section 12 that contains Hydrobon catalyst and the high temperature section 13 that contains asphaltene removal catalyst.To import in the reactor 2 from the effluent of first reactor, wherein make it by low-temperature zone 21 that contains Hydrobon catalyst and the high temperature section 22 that contains asphaltene removal catalyst, form product thus, discharge these product autoreactor 2 bottoms.
Fig. 2 has provided a modification of the inventive method, and wherein the 3rd reactor is present in the reactor 1 described among top Fig. 1 and 2 downstream.In the present embodiment, the effluent of autoreactor 2 imports in the 3rd reactor 3 in the future, wherein make it by low-temperature zone 31 that contains Hydrobon catalyst and the high temperature section 32 that contains asphaltene removal catalyst, form product thus, discharge these product autoreactor 3 bottoms.
Fig. 3 has provided the another modification of the inventive method, the reactor 2 that wherein only contains Hydrobon catalyst is arranged between reactor 1 and the reactor 3, reactor 1 comprises the low-temperature zone 11 that contains Hydrodemetalation catalyst, the medium temperature section 12 that contains Hydrobon catalyst and the high temperature section 13 that contains asphaltene removal catalyst from inlet to outlet, reactor 3 comprises low-temperature zone 31 that contains Hydrobon catalyst and the high temperature section 32 that contains asphaltene removal catalyst from inlet to outlet, form product thus, discharge these product autoreactor 3 bottoms.
Fig. 4 has provided a modification again of the inventive method, and wherein the 3rd reactor is present in the reactor 1 described among top Fig. 1 and 2 downstream.In the present embodiment, the effluent of autoreactor 2 imports in the 3rd reactor 3 in the future, wherein makes it pass through Hydrobon catalyst, forms product thus, and discharge these product autoreactor 3 bottoms.
In all these embodiments, if between reactor, there is stripper, preferably all effluents or all liq effluent are imported in another reactor.
The volume ratio of Hydrodemetalation catalyst layer, Hydrobon catalyst layer and asphaltene removal catalyst layer is 3-50: 30-95: 2-30, more preferably 5-45: 35-95: 2-25 in preferred the first reactor.
The volume ratio of Hydrobon catalyst layer and asphaltene removal catalyst layer is 60-97: 3-40, more preferably 65-97: 3-35 in preferred the second reactor.
If need, can have at the top of the second reactor and non-essential another reactor limited amount scale removal catalyst. Scale removal catalyst is known to persons of ordinary skill in the art. If scale removal catalyst exists, then its amount of application is generally the 1-3 % by weight.
As mentioned above, can arrange in the downstream of the second reactor the 3rd reactor or even further reactor, namely contain the 3rd reactor of Hydrobon catalyst and asphaltene removal catalyst or other reactor from entrance to outlet. In the 3rd reactor and other reactor, Hydrobon catalyst is identical with the top scope that the second reactor is provided with the preferred volume ratio scope of asphaltene removal catalyst.
The inventive method is particularly suitable for the hydrotreatment of heavy hydrocarbon feeds. The method be particularly suitable for hydrotreatment wherein at least 40 % by weight, preferably at least 60 % by weight are seethed with excitement more than 538 ℃ (1000 °F) and are comprised the heavy hydrocarbon feeds of at least 0.1 % by weight, preferred at least 1 % by weight sulphur and at least 5 % by weight Kang Laxun carbon residues. Sulfur content in the raw material can be higher than 2 % by weight. Its Kang Laxun carbon residue content can be higher than 8 % by weight, preferably is higher than 10 % by weight. This raw material will comprise metal pollutant such as nickel and vanadium. The amount of these metals is generally at least 15 ppm by weight, and more preferably at least 30 ppm by weight are based on the calculation of total of Ni and V.
Suitable raw material comprises atmospheric residue, and vacuum residue is mixed with gasoline, vacuum gasoline, coking watt silk oil, crude oil, shale oil, tar sand oils, solvent-deasphalted oils, coal liquefaction wet goods residue. These raw materials are generally atmospheric residue (AR), vacuum residue (VR) and its mixture.
The Hydrodemetalation catalyst that is used for the inventive method comprises the group vib metal component that is carried on the porous oxide carrier usually, preferred molybdenum. This catalyst can comprise also can not comprise VIII family metal component, and preferred nickel and/or cobalt are considered economy and performance, more preferably nickel. The amount of group vib metal component is generally the 1.5-20 % by weight, and more preferably the 4-16 % by weight is pressed trioxide and calculated. If VIII family metal component is present in the Hydrodemetalation catalyst, then its amount is generally the 0.3-6 % by weight, preferred 1-5 % by weight.
This Hydrodemetalation catalyst is loaded on the porous oxide carrier. This carrier preferably comprises the aluminium oxide of at least 50 % by weight, and surplus is made of one or more the oxide in silicon, titanium or the zirconium. This carrier preferably contains at least 75 % by weight, the more preferably aluminium oxide of at least 95 % by weight. This Hydrodemetalation catalyst also can comprise other composition that is applicable in the Hydrodemetalation catalyst known in the art, comprises phosphorus, boron, alkaline components and alkaline earth metal component.
The total pore volume that this Hydrodemetalation catalyst has is generally 0.2-1.4ml/g, preferred 0.4-1.2 ml/g, more preferably 0.5-0.9ml/g. The surface area that this Hydrodemetalation catalyst has is 50-250 m2/ g, preferred 80-200m2/ g, more preferably 100-180m2/ g. If the surface area of this catalyst is too low, then catalytic activity is not enough. If the surface area of this catalyst is too high, then the average pore size of catalyst may be too low. In this context, the average pore size of catalyst be defined as pore volume half be present in the hole of diameter greater than this value, and second half of pore volume is present in diameter less than the aperture in the hole of this value. Being used for the average pore size that the Hydrodemetalation catalyst of the inventive method has usually is 10-35 nm, preferred 15-30nm, more preferably 20-30nm, further more preferably 24-30nm.
The Hydrodemetalation catalyst that is used for the inventive method preferably have be lower than 15%, the pore volume more preferably less than 10% is present in the hole of diameter less than 100 .
Be applicable to that Hydrodemetalation catalyst of the present invention is known in the art.They for example with trade mark KFR 10, KFR 20, KFR 22 and KG 5 available from Nippon Ketjen Co.Ltd.
The Hydrobon catalyst that is used for the inventive method comprises the group vib metal component that is carried on the porous oxide carrier usually, preferred molybdenum, and VIII family metal component, preferred nickel and/or cobalt, more preferably nickel.The amount of group vib metal component is generally 9-30 weight %, and more preferably 10-27 weight % presses trioxide and calculates.The amount of VIII family metal component is generally 2-12 weight %, more preferably 2-8 weight %.
This Hydrobon catalyst is loaded on the porous oxide carrier.This carrier preferably comprises the aluminum oxide of at least 50 weight %, and surplus is made of one or more the oxide compound in silicon, titanium or the zirconium.This carrier preferably contains at least 75 weight %, the more preferably aluminum oxide of at least 95 weight %.This Hydrobon catalyst also can comprise limited amount other composition that is applicable to Hydrobon catalyst known in the art, comprises phosphorus, boron, alkaline components and alkaline earth metal component.
The total pore volume that this Hydrobon catalyst has is generally 0.2-1.4ml/g, preferred 0.4-1.2ml/g, more preferably 0.5-0.9ml/g.The surface-area that this Hydrobon catalyst has is 50-400m
2/ g, preferred 100-300m
2/ g, more preferably 200-300m
2/ g.If the surface-area of this catalyzer is too low, then the catalytic activity deficiency.If the surface-area of catalyzer is too high, then the mean pore size of catalyzer may be too low.Being used for the mean pore size that the Hydrobon catalyst of the inventive method has usually is 5-20nm, preferred 7-15nm, more preferably 7-20nm.
Be applicable to that Hydrobon catalyst of the present invention is known in the art.They for example with trade mark KFR 70, KFR 72 and KFR 70B available from Nippon Ketjen Co.Ltd.
Be used for first reactor Hydrobon catalyst, being used for the Hydrobon catalyst of second reactor and being used for any Hydrobon catalyst of any other reactor can be identical or different.
The asphaltene removal catalyst that is used for the inventive method comprises the group vib metal component that is carried on the porous oxide carrier usually, preferred molybdenum, and VIII family metal component, preferred nickel and/or cobalt, more preferably nickel.The amount of group vib metal component is generally 2-20 weight %, and more preferably 4-16 weight % presses trioxide and calculates.If the group vib metal content is too low, then activity of such catalysts reduces.If the group vib metal content is too high, then activity will can further not improved.The amount of VIII family metal component is generally 0.5-6 weight %, more preferably 1-5 weight %.If VIII family metal content is too low, then activity of such catalysts reduces.If VIII family metal content is too high, then activity will can further not improved.
This asphaltene removal catalyst is loaded on the porous oxide carrier.This carrier preferably comprises the aluminum oxide of at least 50 weight %, and surplus is made of one or more the oxide compound in silicon, titanium or the zirconium.This carrier preferably contains at least 75 weight %, the more preferably aluminum oxide of at least 95 weight %.This asphaltene removal catalyst also can comprise limited amount other composition known in the art, comprises phosphorus, boron, alkaline components and alkaline earth metal component.
The total pore volume that this asphaltene removal catalyst has is generally 0.4ml/g at least, preferably 0.55ml/g at least.Pore volume is generally 1.4ml/g at the most, preferred 1.2ml/g at the most, more preferably 9ml/g at the most.The surface-area that this asphaltene removal catalyst has is 50m at least
2/ g and 200m at the most
2/ g, preferred 100-180m
2/ g.If the surface-area of catalyzer is too low, then the catalytic activity deficiency.If the surface-area of catalyzer is too high, then the mean pore size of catalyzer may be too low.It is 10-35nm that the asphaltene removal catalyst that is used for the inventive method has mean pore size usually, preferred 15-30nm, more preferably 18-28nm.If mean pore size is too low, then bitum decompositions is not enough, may over-hydrogenation take place and increases sludge formation.If mean pore size is too high, then the bituminous matter rate of decomposition also may reduce, intrinsic formation sludge.
The asphaltene removal catalyst that is used for the inventive method preferably have be lower than 15%, the pore volume more preferably less than 10% is present in the hole of diameter less than 100 .
At diameter is that the pore volume that this asphaltene removal catalyst has usually is 0.3ml/g or lower in 100nm or the bigger hole, preferred 0.2ml/g or lower.If it is too high to be present in the amount of the pore volume in this scope, then bituminous matter is decomposed and as the loss of equilibrium between the resin of its solvent, is easy to form sludge.In addition, if it is too high to be present in the amount of the pore volume in this scope, then the physical strength of catalyzer will reduce.
Be applicable to that asphaltene removal catalyst of the present invention is known in the art.They for example with trade mark KFR 10, KFR 20, KFR 22 and KG 5 available from Nippon Ketjen Co.Ltd.
Be used for first reactor asphaltene removal catalyst, being used for the asphaltene removal catalyst of second reactor and being used for any asphaltene removal catalyst of any other reactor can be identical or different.
From the above description as seen, it is very similar to be used for the asphaltene removal catalyst and the Hydrodemetalation catalyst of the inventive method.This means that the Hydrodemetalation catalyst that is used for the inventive method within the scope of the present invention is identical with asphaltene removal catalyst.
The Hydrobon catalyst that is used for the inventive method always is different from Hydrodemetalation catalyst and asphaltene removal catalyst.More specifically, the group vib metal content that Hydrobon catalyst has is preferably up to few 3 weight % than the group vib metal content of Hydrodemetalation catalyst and the group vib metal content height at least 2 weight % of asphaltene removal catalyst, presses trioxide and calculates.
In addition, the mean pore size of Hydrobon catalyst is than the little 1nm at least of mean pore size of the mean pore size and the asphaltene removal catalyst of Hydrodemetalation catalyst, preferred 2nm at least, more preferably 3nm at least.
Granules of catalyst can have shape and size common in the prior art.Therefore, these particles can be sphere, cylindrical or polylobal, and its diameter range can be 0.5-10mm.Preferred diameter is 0.5-3mm, preferred 0.7-2mm, and for example 1.2-1.5mm and length are 1.5-10mm, for example the particle of 2.5-4.5mm.Because they cause the pressure reduction in the hydrodemetallation (HDM) operation.Therefore preferred polylobal particle.
If need, the little amount of catalyst that is used for one or more reactor top layers can have different particle shapes and size, to regulate the feedstream by reactor.
As is common in the prior art, various types of catalyzer can be present in the single bed in the unit, or are present in a plurality of beds on another that contain the same type catalyzer.
The method of the catalyzer that uses in preparation the inventive method is unimportant, for example, a kind of appropriate preparation method is described below.
The exemplary production method that is used to prepare the support of the catalyst that comprises aluminum oxide is with sodium aluminate and Tai-Ace S 150 co-precipitation.With the gel drying that obtains, extrude and calcine, obtain salic carrier.Before precipitation, the precipitation during and the precipitation after can optionally add other component such as silicon-dioxide.For example, a kind of method for preparing alumina gel is described below.The alkaline solution that at first adds sodium aluminate, aluminium hydroxide or sodium hydroxide etc. in the jar of tap water or warm water is housed, the acidic aluminum solution that adds Tai-Ace S 150 or aluminum nitrate etc. again is to mix.The hydrogen ion concentration of mixing solutions (pH) changes along with reaction process.Preferably when acidic aluminum solution added, pH was 7-9, and during mixing temperature is 60-75 ℃.Then this mixture was kept 0.5-1.5 hour usually preferred 40-80 minute under this temperature.
In next step, gel is separated from solution, and carried out the carrying out washing treatment of any industrial use, as using the carrying out washing treatment of tap water or hot water,, mainly be salt from gel, to remove impurity.Then with this gel in a manner known in the art for example by extrude, beadization or granulation formation be particle.
At last with the particle drying and the calcining that are shaped.Dry under the temperature of room temperature to 200 ℃, in the presence of air, carry out usually usually.Calcining was carried out in the presence of air 30 minutes to 6 hours under 300-950 ℃, preferred 600-900 ℃ temperature usually usually.If need, calcining can be carried out in the presence of steam to influence the crystal growth in the oxide compound.
By aforementioned production method, can obtain to have and make catalyzer have the carrier of the performance of top given surface-area, pore volume and pore size distribution characteristic.Surface-area, pore volume and pore size distribution characteristic can be according to the known modes of those skilled in the art, for example by mixing or shaping stage adds acid as nitric acid, acetate or formic acid or other compound as the molding auxiliary agent or by regulating by the mode that adds or remove the water-content of the adjustment gel that anhydrates.
Group vib metal component and suitable, VIII family metal component or other component such as phosphorus can for example add in the support of the catalyst by dipping and/or by joining in the carrier substance before being configured as particle in a usual manner.To this, think at present preferably at first to prepare carrier, after this carrier drying and calcining, catalytic specie is added in the carrier then.Metal component can the suitable precursor form, preferably by adding in the catalyst composition with the acid or alkaline dipping solution impregnated catalyst that comprises suitable metal precursor.For the group vib metal, can mention that Ammonium Heptamolybdate, ammonium dimolybdate and ammonium tungstate are as suitable precursor.Also can use other compound, as oxide compound, oxyhydroxide, carbonate, nitrate, muriate and organic acid salt.For VIII family metal, suitable precursor comprises oxide compound, oxyhydroxide, carbonate, nitrate, muriate and organic acid salt.Carbonate and nitrate are specially suitable.Dipping solution is if the words of using can comprise other compound such as the organic acid of use known in the art, for example citric acid, ammoniacal liquor, aqueous hydrogen peroxide solution, glyconic acid, tartrate, oxysuccinic acid or EDTA (ethylenediamine tetraacetic acid (EDTA)).Those skilled in the art should be understood that there are a lot of modification in this method.Therefore, can apply a plurality of impregnation steps, dipping solution to be used comprises treats sedimentary one or more component precursors or its part.Can use immersion process, spray method etc. to replace impregnation technology.Repeatedly flooding, under the situation of immersion etc., can between these steps, carry out drying and/or calcining.
After adding metal in the catalyst composition, with its optionally for example under room temperature to 200 ℃ in airflow dry about 0.5-16 hour, subsequently usually in air 200-800 ℃, preferred 450-700 ℃ of calcining about 1-6 hour down, preferably 1-3 hour.Carrying out the exsiccant purpose is to remove sedimentary water with physics mode.Carry out the incinerating purpose and be to make to small part, preferably all metal component precursor conversion become oxide form.
May it is desirable for before catalyzer is used for the hydrotreatment hydrocarbon feed catalyzer, the group vib and the non-essential VIII family metal component that are about to be present in wherein are converted into sulphided form.This can pass through other usual manner, is for example undertaken by catalyzer is contacted with the sulfur-bearing raw material with hydrogen in reactor at elevated temperatures, or contacts with the mixture of hydrogen and hydrogen sulfide and to carry out.Can also not carry out prevulcanized at the scene.
In this manual, term " group vib metal " and " VIII family metal " are with reference to the periodic table of elements (CAS system) of Chemical Abstracts Service use.Specific surface area is passed through nitrogen (N with the BET method
2) determining adsorption.The mercury porosity-meter Autopore II (trade(brand)name) that the mensuration of total pore volume and pore size distribution is produced with for example Micrometrics is by being that 140 degree and surface tension are that mercury penetration method under 480 dyne/cm carries out at contact angle.
Embodiment:
Choose three kinds of catalyzer to be used for present embodiment.
Hydrodemetallation (HDM) (HDM) catalyzer comprises the molybdenum that is carried on 9 weight % on the alumina supporter and the nickel of 2 weight %, and the two all calculates by oxide compound.The mean pore size that this catalyzer has is 180 .
Hydrogenating desulfurization (HDS) catalyzer comprises the molybdenum that is carried on 12 weight % on the alumina supporter and the nickel of 3 weight %, and the two all calculates by oxide compound.The mean pore size that this catalyzer has is 120 .
Asphaltene removal (HDAsp) catalyzer comprises the molybdenum that is carried on 8.0 weight % on the alumina supporter and the nickel of 2.2 weight %, and the two all calculates by oxide compound.The mean pore size that this catalyzer has is that 260 , surface-area are 130m
2/ g, total pore volume are 0.8ml/g and are that pore volume in 100 and the bigger hole is 0.25ml/g at diameter.
The raw material that uses in the present embodiment is South Sea atmospheric residue, and it has following character:
| Sulphur | 0.2 weight % |
| Nitrogen | 3000 ppm by weight |
| Metal (nickel+vanadium) | 70 ppm by weight |
| The Kang Laxun carbon residue | 7 weight % |
| Bituminous matter 1 | 2.5 weight % |
| Density (15 ℃) | 0.93g/ml |
| Distillation performance ASTM-D 5307 | |
| Initial boiling point | 301℃ |
| 50 weight % | 563℃ |
| 70 weight % | 624℃ |
1Be insoluble to the material in the normal heptane
In the mini-reactor system that forms by three reactors that are connected in series, fill the catalyzer of choosing.The filling that is used for the reactor of the embodiment of the invention 1 and Comparative Examples provides as follows:
| | Comparative Examples | |
| First reactor | HDM catalyzer-20 volume % HDS catalyzer-55 volume % HDAsp catalyzer-25 volume % | HDM catalyzer-20 volume % HDS catalyzer-80 volume % |
| Second reactor | HDS catalyzer-75 volume % HDAsp catalyzer-25 volume % | HDS catalyzer-100 volume % |
| The 3rd reactor | HDS catalyzer-95 volume % HDAsp catalyzer-5 volume % | HDS catalyzer-100 volume % |
After reactor assembly filled with corresponding catalyzer, catalyzer is vulcanized by it is contacted with the petroleum naphtha (LGO) that contains 2.5 weight % dimethyl disulphides (DMDS) in a conventional manner, and be that 16.5MPa, liquid hourly space velocity (LHSV) are 0.3h at pressure above-mentioned raw materials
-1With hydrogen and raw material ratio (H
2/ oil ratio example) imports in the reactor assembly down for 850Nl/l.The Kang Laxun carbon residue content is 3.0 weight % to the conditioned reaction temperature in the product oil to reach, wherein in each reactor, the temperature in second bed is higher than the temperature in first, simultaneously, be suitable for, the temperature in the 3rd bed is higher than second temperature in the bed.The time that test is carried out is 200 days.
For asphaltene removal catalyst wherein be present in embodiment in each the high temperature bottom section in three reactors after 1,200 day this method still operate well and still can continue after this.Yet, being present in Comparative Examples in each the high temperature bottom section in three reactors for no asphaltene removal catalyst, this method has to interrupt at 135 days, because reactor is stopped up by sludge.
Following table has provided the temperature of each catalyst layer in embodiment 1 and the Comparative Examples.
| Embodiment 1 (the 200th day) | Comparative Examples (the 135th day) | |
| First reactor | 405 ℃ of 398 ℃ of HDAsp catalyzer of 390 ℃ of HDS catalyzer of HDM catalyzer | 400 ℃ of 390 ℃ of HDS catalyzer of HDM catalyzer |
| Second reactor | 422 ℃ of 413 ℃ of HDAsp catalyzer of HDS catalyzer | 413 ℃ of HDS catalyzer |
| The 3rd reactor | 423 ℃ of 421 ℃ of HDAsp catalyzer of DS catalyzer | 422 ℃ of HDS catalyzer |
The method of embodiment 1 and Comparative Examples is operated according to the condition that the Kang Laxun carbon residue amount in the product remains 3.0 weight %.This means convention, temperature of reaction is slowly raise with the compensate for catalyst passivation, thus the Kang Laxun carbon residue amount in the product is remained desirable value according to this area hydroprocessing technique.
Fig. 4 shows the variation of the average reaction temperature in the inventive method and Comparative Examples procedure, and wherein the Kang Laxun carbon residue content in the product keeps constant.As can be seen, for the method for the embodiment of the invention 1, temperature raises stable, is lower than 0.8 ℃ in every month, and on the contrary, for Comparative Examples, before off-test, temperature raises and reaches every month 2 ℃.
Obviously, even the Kang Laxun carbon residue content of product is identical, but asphaltene removal catalyst has guaranteed to form less sludge in the existence of the high temperature bottom of hydrotreating reactor, and this makes that the unit is still less blocked and operation is more permanent and more stable.The existence of asphaltene removal catalyst seems also to make method more stable, and this can find out from being that the rising of the necessary temperature of reaction of 3.0 weight % is low for the Kang Laxun carbon residue content that keeps product.
Be not bound by any theory although do not wish, but the inventor believes: asphaltene removal catalyst has guaranteed that bituminous matter is decomposed and well balanced as between the resin of its solvent in the existence of the high temperature bottom of hydrotreating reactor, causes sludge to form thus and reduces.On the other hand, it is believed that in Comparative Examples that when not having asphaltene removal catalyst, the resin that is used as bitum solvent is hydrogenated.As a result, bituminous matter is insoluble in the hydrocarbon feed, causes forming sludge.The existence of sludge is because of forming the passivation that coke causes catalyzer conversely again on catalyzer.
Claims (10)
1. the method for the hydrotreatment of heavy hydrocarbon raw material of at least two reactors of a use, wherein heavy hydrocarbon feeds is carried out following steps successively:
In first hydrotreating reactor, carry out hydrotreatment, wherein it is carried out hydrodemetallation (HDM) step, hydrodesulfurisationstep step and asphaltene removal step successively, wherein hydrodesulfurisationstep step is higher than in temperature under the temperature of described hydrodemetallation (HDM) step and carries out, asphaltene removal step is higher than in temperature under the temperature of described hydrodesulfurisationstep step carries out
Carry out hydrotreatment in second hydrotreating reactor, wherein it is carried out hydrodesulfurisationstep step and asphaltene removal step successively, back one step is higher than in temperature under the temperature of described hydrodesulfurisationstep step carries out.
2. the process of claim 1 wherein that hydrodemetallation (HDM) step use Hydrodemetalation catalyst carries out, hydrodesulfurisationstep step uses Hydrobon catalyst to carry out, and asphaltene removal step uses asphaltene removal catalyst to carry out.
3. the method for claim 2, wherein Hydrodemetalation catalyst comprises the group vib metal component that is carried on the porous oxide carrier, and the surface-area that this catalyzer has is 50-200m
2/ g and mean pore size are 10-35nm; Hydrobon catalyst comprises group vib metal component and the VIII family metal component that is carried on the porous oxide carrier, and the surface-area that this catalyzer has is 50-400m
2/ g and mean pore size are 5-20nm; And asphaltene removal catalyst comprises the group vib metal component that is carried on the porous oxide carrier, and the surface-area that this catalyzer has is 50-200m
2/ g and mean pore size are 10-35nm.
4. claim 2 or 3 method, wherein the group vib metal content that has of Hydrobon catalyst is than the group vib metal content of Hydrodemetalation catalyst and the group vib metal content height at least 2 weight % of asphaltene removal catalyst.
5. any one method of claim 2-4, wherein the mean pore size that has of Hydrobon catalyst is than the little 1nm at least of mean pore size of the mean pore size and the asphaltene removal catalyst of Hydrodemetalation catalyst.
6. any one method of claim 1-5, wherein be provided with the 3rd hydrotreating reactor in the downstream of second hydrotreating reactor, in the 3rd hydrotreating reactor, second hydrotreating reactor carry out hydrodesulfurisationstep step and asphaltene removal step successively to the small part effluent, back one step is higher than in temperature under the temperature of described hydrodesulfurisationstep step carries out.
7. any one method of claim 1-5, wherein be provided with the 3rd hydrotreating reactor in the downstream of second hydrotreating reactor, in the 3rd hydrotreating reactor, second hydrotreating reactor carry out hydrodesulfurisationstep step to the small part effluent.
8. any one method of claim 1-5, wherein between first hydrotreating reactor and second hydrotreating reactor, be provided with other hydrotreating reactor, in this other hydrotreating reactor, first hydrotreating reactor carry out hydrodesulfurisationstep step to the small part effluent, the importing in second hydrotreating reactor to the small part effluent of the hydrotreating reactor that this is other.
9. any one method of front claim, wherein raw material is a heavy hydrocarbon feeds, its at least 50 weight % is in boiling more than 538 ℃ and comprise to the sulphur of 2 weight % and the Kang Laxun carbon residue of at least 5 weight %.
10. any one method of front claim, wherein in first reactor, temperature in the hydrodesulfurizationsection section is than at least 2 ℃ of the temperature height in front-end hydrogenation demetalization section, in first, second and non-essential other reactor, the temperature in the asphaltene removal section is than at least 2 ℃ of each temperature height in the front-end hydrogenation desulfurization section.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP169868/2002 | 2002-06-11 | ||
| JP2002169868A JP2004010857A (en) | 2002-06-11 | 2002-06-11 | Method for hydrogenating hydrocarbon heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1668723A true CN1668723A (en) | 2005-09-14 |
Family
ID=29727749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038165295A Pending CN1668723A (en) | 2002-06-11 | 2003-06-05 | A process for the hydroprocessing of heavy hydrocarbon feeds using at least two reactors |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20060060509A1 (en) |
| EP (1) | EP1511825A1 (en) |
| JP (1) | JP2004010857A (en) |
| KR (1) | KR20050010878A (en) |
| CN (1) | CN1668723A (en) |
| AU (1) | AU2003236725A1 (en) |
| CA (1) | CA2489184A1 (en) |
| WO (1) | WO2003104359A1 (en) |
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| CN102876372A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Single-stage series hydrofinishing method of diesel oil |
| CN103059931A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
| CN109694733A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | The method and system of boiling bed residual oil hydrocracking |
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| US7736490B2 (en) | 2003-12-19 | 2010-06-15 | Shell Oil Company | Systems, methods, and catalysts for producing a crude product |
| FR2904324B1 (en) * | 2006-07-27 | 2012-09-07 | Total France | METHOD FOR HYDROPROCESSING A GAS LOAD, HYDROTREATING REACTOR FOR CARRYING OUT SAID METHOD, AND CORRESPONDING HYDROREFINING UNIT. |
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| WO2009073436A2 (en) * | 2007-11-28 | 2009-06-11 | Saudi Arabian Oil Company | Process for catalytic hydrotreating of sour crude oils |
| WO2010009077A2 (en) | 2008-07-14 | 2010-01-21 | Saudi Arabian Oil Company | Process for the treatment of heavy oils using light hydrocarbon components as a diluent |
| US20100018904A1 (en) * | 2008-07-14 | 2010-01-28 | Saudi Arabian Oil Company | Prerefining Process for the Hydrodesulfurization of Heavy Sour Crude Oils to Produce Sweeter Lighter Crudes Using Moving Catalyst System |
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| US4054508A (en) * | 1975-02-21 | 1977-10-18 | Mobil Oil Corporation | Demetalation and desulfurization of residual oil utilizing hydrogen and trickle beds of catalysts in three zones |
| US4431525A (en) * | 1982-04-26 | 1984-02-14 | Standard Oil Company (Indiana) | Three-catalyst process for the hydrotreating of heavy hydrocarbon streams |
| US4431526A (en) * | 1982-07-06 | 1984-02-14 | Union Oil Company Of California | Multiple-stage hydroprocessing of hydrocarbon oil |
| US4657664A (en) * | 1985-12-20 | 1987-04-14 | Amoco Corporation | Process for demetallation and desulfurization of heavy hydrocarbons |
| US5744025A (en) * | 1997-02-28 | 1998-04-28 | Shell Oil Company | Process for hydrotreating metal-contaminated hydrocarbonaceous feedstock |
| JP2001003066A (en) * | 1999-06-24 | 2001-01-09 | Idemitsu Kosan Co Ltd | Production of desulfurized fuel oil |
-
2002
- 2002-06-11 JP JP2002169868A patent/JP2004010857A/en active Pending
-
2003
- 2003-06-05 KR KR10-2004-7020075A patent/KR20050010878A/en not_active Application Discontinuation
- 2003-06-05 EP EP03735587A patent/EP1511825A1/en not_active Withdrawn
- 2003-06-05 CA CA002489184A patent/CA2489184A1/en not_active Abandoned
- 2003-06-05 WO PCT/EP2003/006033 patent/WO2003104359A1/en not_active Application Discontinuation
- 2003-06-05 AU AU2003236725A patent/AU2003236725A1/en not_active Abandoned
- 2003-06-05 US US10/517,100 patent/US20060060509A1/en not_active Abandoned
- 2003-06-05 CN CNA038165295A patent/CN1668723A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876372A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Single-stage series hydrofinishing method of diesel oil |
| CN102876372B (en) * | 2011-07-11 | 2014-10-15 | 中国石油化工股份有限公司 | Single-stage series hydrofinishing method of diesel oil |
| CN103059931A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
| CN103059931B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
| CN109694733A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | The method and system of boiling bed residual oil hydrocracking |
| CN109694733B (en) * | 2017-10-23 | 2021-02-09 | 中国石油化工股份有限公司 | Process and system for hydrocracking ebullated bed resid |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060060509A1 (en) | 2006-03-23 |
| EP1511825A1 (en) | 2005-03-09 |
| KR20050010878A (en) | 2005-01-28 |
| JP2004010857A (en) | 2004-01-15 |
| CA2489184A1 (en) | 2003-12-18 |
| AU2003236725A1 (en) | 2003-12-22 |
| WO2003104359A1 (en) | 2003-12-18 |
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