CN113122311B - Hydrofining catalyst grading method - Google Patents
Hydrofining catalyst grading method Download PDFInfo
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- CN113122311B CN113122311B CN201911418283.0A CN201911418283A CN113122311B CN 113122311 B CN113122311 B CN 113122311B CN 201911418283 A CN201911418283 A CN 201911418283A CN 113122311 B CN113122311 B CN 113122311B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000010779 crude oil Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 19
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 9
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008021 deposition Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000004939 coking Methods 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LCSNMIIKJKUSFF-UHFFFAOYSA-N [Ni].[Mo].[W] Chemical compound [Ni].[Mo].[W] LCSNMIIKJKUSFF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011219 quaternary composite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/613—10-100 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrofining process. Mixing raw oil with hydrogen, and passing through a hydrofining reaction zone to obtain a hydrofining reaction effluent; the hydrofining reaction zone comprises a plurality of hydrofining catalyst beds, the metal content of the catalyst in the hydrofining catalyst beds is sequentially increased according to the contact sequence of the hydrofining catalyst beds and the raw oil, the total acid content of the catalyst is sequentially increased, the L acid content is sequentially increased, and the fluorine content is sequentially reduced. The method is particularly suitable for the hydrocracking pretreatment or hydrofining process, can effectively relieve the polymerization and temperature runaway problems of polycyclic aromatic hydrocarbon caused by higher activity and temperature rise of the first bed catalyst while ensuring the effects of hydrodesulfurization and hydrodenitrogenation, and prolongs the service life of the catalyst and the operation period of the device.
Description
Technical Field
The invention relates to a preparation method and a grading method of a hydrofining catalyst. The method is particularly suitable for the hydrocracking pretreatment process, and can reduce the carbon deposition amount of the catalyst and the pressure drop of the reactor while ensuring hydrodesulfurization, denitrification and dearomatization, thereby prolonging the running period of the hydrogenation device.
Background
With the trend toward heavy and poor crude oils, crude oil processing is increasingly difficult to obtain acceptable products. Hydrogenation technology has been widely used in refineries as a clean fuel production technology. The hydrotreating process of the refinery mainly comprises a naphtha prehydrogenation technology, a aviation kerosene hydrogenation technology, a diesel oil hydrofining technology, a wax oil hydrogenation pretreatment technology, a hydrocracking technology, a residual oil hydrogenation technology, fluidized bed hydrocracking, a slurry bed hydrogenation technology and the like. Among these techniques, hydrofining catalysts play an important role in oil cleanliness. The hydrofining agent mainly removes sulfur, nitrogen, aromatic hydrocarbon, oxygen, metal, colloid, asphaltene and the like in the raw oil. The removal of sulfur, nitrogen and oxygen atoms in a proper range has little influence on the activity and stability of the catalyst. And the removal of aromatic hydrocarbon, metal, colloid and asphaltene has a great influence on the activity and service cycle of the hydrofining catalyst. Metals in the feedstock are removed which can cause a pressure drop across the bed or chemically poison the catalyst. Polycyclic aromatic hydrocarbons in the raw materials are easy to condense carbon on the outer surface of the catalyst to cover the surface active center, thereby causing bed pressure drop and reduction of the activity of the catalyst. The industrial wax oil hydrogenation device is frequently skimmed due to the pressure drop problem, mainly because the first bed layer of the hydrofining reactor is preferentially contacted with the poor-quality raw material with high aromatic hydrocarbon and high sulfur nitrogen, metal and polycyclic aromatic hydrocarbon in the raw material are easily accumulated on the surface of the catalyst of the bed layer, the inner pore channel and the outer pore channel of the catalyst are blocked, the diffusion and the flowing of the raw material are hindered, the pressure drop problem is caused, the abnormal shutdown of the wax oil hydrogenation device is forced, and the enterprise benefit is seriously influenced.
Therefore, in order to solve the above problems, a hydrofining catalyst with high activity and stability needs to be developed, and a reasonable grading system needs to be made for the properties of material flows in different reaction areas in a hydrofining reactor, so that the desulfurization, denitrification and dearomatization can be performed to the maximum extent, and the carbon deposition and poisoning of the catalyst can be reduced, thereby increasing the service cycle of the device and the economic benefits of enterprises.
For the hydrocracking pretreatment process, the inferior raw material is directly contacted with the hydrofining catalyst on the upper bed layer after simple traditional carbon residue and metal removal, and the aromatic hydrocarbon content, especially the alkaline nitrogen content, in the material flow is higher, and after being combined with the L acid center in the hydrofining catalyst, the inferior raw material is easy to coke on the surface of the catalyst. Along with the increase of the saturation depth of aromatic hydrocarbon and the increase of the removal rate of basic nitrogen, the carbon content of the lower bed lamination is reduced in sequence. This causes the most serious coking of carbon deposit on the upper bed layer of the hydrofining reactor, which causes the pressure drop of the reactor to increase. In addition, in the hydrorefining reaction zone, the reactions of desulfurization and denitrification are preferentially carried out, and the removal of aromatic hydrocarbon is mainly concentrated in the lower bed layer. In the whole hydrogenation refining process, the hydrodesulfurization reaction is easiest, and the hydrodenitrogenation and dearomatization are difficult. The proper acid properties of the hydrofinishing catalyst, and particularly the proper B acid content, are very beneficial for the denitrification reaction. The traditional industrial hydrorefining catalyst adopts a single carrier, active metal components, pore diameters, morphology and bulk density, and obviously cannot ensure the long-period operation of a hydrocracking device, so that a hydrorefining reactor is reasonably graded from the physicochemical property, particularly the acid property, of the carrier catalyst according to the influence mechanism of the acid type on hydrodenitrogenation and coking reactions, so as to achieve the purposes of slowing down the coking of the catalyst and reducing the pressure drop of the reactor.
In the hydrocracking technology, the hydrocracking catalyst grading is reported more, but the hydrofinishing catalyst grading is reported less. CN 103059983A discloses a diesel hydrorefining catalyst combined filling method. Raw oil and hydrogen are mixed and then enter four reaction zones with different functions, hydrogenation catalysts with different metal types, different metal contents and different acid amounts are filled in each reaction zone, and qualified diesel oil products can be obtained after reaction effluents pass through a fractionation system. The invention can design different types of hydrogenation catalysts according to different metals on the saturation capacity of aromatic hydrocarbon, and realizes win-win of activity and stability. The method is suitable for diesel raw oil with high sulfur content and low nitrogen content, so as to fully exert the hydrogenation performance of nickel-molybdenum-tungsten active metal and the high-temperature stability of cobalt-molybdenum active metal.
CN 102876365A describes a grading method of a catalyst for hydrofining inferior distillate oil, a reactor is divided into three reaction zones, and a hydrogenation protective agent is filled in the first reaction zone; a second-stage reaction zone is filled with a hydrofining agent A, quaternary composite oxidation is adopted as a carrier, and ternary metal is loaded; and a hydrofining agent B is filled in the third reaction zone, and a ternary composite oxide is adopted as a carrier and loaded with ternary metal. The invention matches pore volume, specific surface, surface acid amount and metal components, can realize ultra-deep desulfurization effect, and finally obtains the ultra-low sulfur diesel oil with sulfur content meeting Euro IV standard.
CN 108393096A discloses a hydrodesulfurization catalyst, a grading combination method of a hydrofining catalyst and application thereof. The method modulates the pore diameter property and the acid property of the inside and the outside of the catalyst by synthesizing the mesoporous and microporous composite material so as to improve the activity of the catalyst. The catalyst prepared by the method has a multi-stage pore channel structure, is properly matched in acidity, effectively utilizes the active center of the catalyst, and improves the hydrofining activity of the catalyst. However, the method only starts from the microscopic angle of catalyst synthesis, and further grading is not carried out between reactor beds according to the reaction characteristics of hydrodesulfurization and denitrification, so that the improvement of the stability of the whole reaction system and the extension of the running period of the device are difficult to realize.
Disclosure of Invention
The invention provides an improved wax oil hydrofining process, which aims to solve the technical problem that the top of a catalytic system is easy to coke in the existing wax oil hydrofining process.
The hydrofining catalyst is usually prepared by loading metal oxides containing VIII group and VIB group in the periodic table into a refractory inorganic porous material, generally adopting gamma-alumina as a carrier, preparing a catalyst precursor through an impregnation process, and preparing a finished catalyst through drying and roasting steps. However, the hydrofining catalyst using gamma-alumina as a carrier has the characteristic of more surface hydroxyl groups, so that the acting force of catalyst metal and the gamma-alumina carrier is larger, and the dispersion degree of active metal is not high. In addition, all alumina carriers only have L acid centers, and even if metal is loaded or an auxiliary agent is added, B acid centers of the alumina carriers are still few, so that the requirements of ultra-deep desulfurization and denitrification cannot be met. Introduction of heteropolyacid or NH during catalyst preparation 4 F and the like can effectively increase the central amount of the B acid. For the high-nitrogen raw material, the denitrification capability of the hydrofining agent can be greatly increased after the B acid is introduced.
The invention aims to overcome the defect of single hydrofining agent in the prior art, and provides a grading method for reducing coking and carbon deposition of the hydrofining agent and increasing the overall hydrofining activity, so that the operation period of a hydrocracking device is prolonged, and the enterprise benefit is improved.
A grading method of hydrofining catalyst comprises the following steps:
after being mixed with hydrogen, the wax oil raw oil passes through a hydrofining reaction zone to be in contact reaction with a hydrofining catalyst, so as to obtain a hydrofining reaction effluent; the hydrofining catalyst takes VIII family and/or VIB family metals as active metal components, alumina as a carrier, and an auxiliary agent fluorine is contained in the catalyst;
the hydrofining reaction zone comprises more than two hydrofining catalyst beds, the content of active metal components of the hydrofining catalysts is sequentially increased according to the contact sequence of the hydrofining catalysts and raw oil, the total acid amount of the catalysts is sequentially increased, the L acid amount is sequentially increased, and the fluorine element content is sequentially reduced.
Wherein, the raw oil is conventional diesel oil or wax oil raw material. The distillation range of the raw oil is generally 180 to 550 ℃, and a high-nitrogen raw material having a nitrogen content of 1000. Mu.g/g or more is preferred. When processing inferior raw materials, protective agents including demetallization agents, carbon residue removal agents, silicon capture agents and the like are filled in front of the hydrofining catalyst. The inferior raw oil comprises coker gasoline, coker diesel oil, catalytic diesel oil, coker gas oil, boiling bed wax oil and the like.
The hydrofinishing reaction zone typically comprises from 2 to 6 hydrofinishing catalyst beds, preferably from 3 to 5 hydrofinishing catalyst beds.
In the hydrofining catalyst, the content of active metal components in terms of oxide is 10.0-50.0%, preferably 12.0-45.0% on the basis of the weight of the catalyst; the content of fluorine (F) is generally 1.0 to 15.0%, preferably 2.0 to 10.0%. Wherein the metal in the VIII family is Co and/or Ni, and the metal in the VIB family is W and/or Mo. The total infrared acid amount of the hydrofining catalyst is 0.05-1.0 mmol/L, preferably 0.1-0.8 mmol/L; the L acid content is 0.04-0.70 mmol/L, preferably 0.08-0.60 mmol/L; the molar ratio L acid/B acid is generally from 1.0 to 20.0, preferably from 2.0 to 15.0. The average pore diameter of the catalyst is generally from 0.5 to 30.0 nm, preferably from 4.0 to 20.0 nm; the pore volume is 0.2-1.2 cm 3 A/g, preferably 0.3 to 0.9 cm 3 (iv) g; the particle size is 1.0 to 30.0 mm, preferably 2.0 to 20.0 mm. In the art, the synthesis conditions of alumina and NH are varied during the preparation of the catalyst 4 The introduction amount of F can adjust the total acid, L acid and B acid of the catalyst.
Further, in two adjacent hydrofining catalyst beds, the catalyst of the downstream bed is compared with the catalyst of the upstream bed: the fluorine content is 1.0 to 8.0 percent lower, preferably 1.5 to 5.0 percent lower; the content of the active metal component calculated by oxide is 3.0 to 20.0 percent, preferably 5.0 to 15.0 percent; the total infrared acid amount is 0.05-0.25 mmol/L higher; the acid content of L is 0.05-0.25 mmol/L.
Taking the example that the hydrofining reaction zone comprises three catalyst beds, the F content of the hydrogenation catalyst of the first catalyst bed is generally 8.5-15.0%, the total infrared acid amount is generally 0.20-0.36 mmol/L, and the L acid amount is 0.10-0.28 mmol/L; the mass fraction of F of the second catalyst bed hydrogenation catalyst is generally 6.5-8.4%, the total infrared acid amount is generally 0.36-0.45 mmol/L, and the L acid amount is 0.29-0.39 mmol/L; the mass fraction of F of the third catalyst bed hydrogenation catalyst is generally 1.0-6.4%, the total infrared acid amount is generally 0.45-0.80 mmol/L, and the L acid amount is 0.40-0.70 mmol/L.
The hydrofining agent takes alumina as a carrier. The process for preparing a hydrofinishing catalyst generally comprises: pseudo-boehmite, aluminum sulfate, aluminum isopropoxide, aluminum chloride hexahydrate and the like are used as aluminum sources, and the alumina carrier with different physical and chemical properties is prepared after hydrolysis roasting. In the synthesis process, the physicochemical properties of the carrier, such as the L acid content, the pore diameter and the like, are adjusted by changing the roasting temperature of the alumina carrier. The roasting temperature of the alumina carrier is 400-800 ℃, preferably 500-750 ℃; the average pore diameter of the alumina carrier is generally 0.8-35.0 nm, preferably 6.0-25.0 nm; the pore volume is 0.3-1.5 cm 3 A/g, preferably 0.4 to 1.0 cm 3 (ii)/g; the total infrared acid amount of the alumina carrier is 0.04-1.2 mmol/L, preferably 0.05-1.0 mmol/L. Dipping by using dipping solution containing active metal components, drying and roasting to obtain a hydrofining catalyst intermediate, and then adding NH with certain concentration 4 And drying and roasting the aqueous solution F to obtain the hydrofining catalyst with different acid properties.
According to one embodiment of the present invention, the average pore (diameter) size of the hydrorefining catalyst gradually decreases and the particle size gradually decreases in the order of contact with the feedstock oil. Taking a hydrofining reactor comprising three beds as an example, the specific optimization implementation mode is as follows: the content of metal components of the first bed layer hydrofining agent calculated by metal oxides is 5.0-18.0 w%, the average pore diameter is 14.0-20.0 nm, and the particle size is 10.0-20.0 mm; the metal component of the second bed layer hydrofining agent is 20.0-28.0 w percent calculated by metal oxide, the average pore diameter is 10-14 nm, and the particle size is 6-10 mm; the content of metal components of the hydrofining agent of the third bed layer is 30.0-36.0 w percent calculated by metal oxide, the average pore diameter is 3.0-6.0 nm, and the particle diameter is 2.0-6.0 mm.
The process conditions of the hydrofining reaction zone comprise: the average reaction temperature is 280-450 ℃, preferably 300-420 ℃, and most preferably 330-400 ℃; the partial pressure of the reaction hydrogen is 6 to 20 MPa, preferably 8 to 18MPa, and most preferably 10 to 16 MPa; the volume ratio of the hydrogen to the oil is 300 to 2000 h -1 Preferably 400 to 1800 hours -1 Preferably 600-1200 h -1 The liquid hourly space velocity is 0.1-2 h -1 Preferably 0.2 to 1.8 hours -1 Preferably 0.5 to 1.5 hours -1 。
Compared with the prior art, the method has the beneficial effects that:
(1) The invention deeply explores the relationship between coking and polycyclic aromatic hydrocarbon hydrogenation by researching the coking problem at the top of the reactor of the hydrorefining device and the partition characteristics of the hydrorefining reaction. And grading the total acid amount of the hydrofining catalyst according to the reaction depth of denitrification and polycyclic aromatic hydrocarbon in different reaction areas of the hydrofining device. Along the material flow direction, the total acid amount of the catalyst is gradually increased, the hydrofining activity is also gradually increased, and the problems of polycyclic aromatic hydrocarbon polymerization and temperature runaway caused by high catalyst activity and temperature rise of the first bed layer can be effectively avoided.
(2) Due to the gradual decrease of polycyclic aromatic hydrocarbon along the material flow direction, the coking precursor is gradually reduced. And the B acid center can effectively inhibit polycyclic aromatic hydrocarbon coking. The method of the invention carries out grading on the acid B (fluorine content) and the acid L, along the material flow direction, the acid B quantity is gradually reduced, and the acid L quantity is gradually increased, thereby realizing the stepwise stable saturation of the polycyclic aromatic hydrocarbon, reducing the coking and carbon deposition of a catalyst bed layer, and prolonging the service life of the catalyst and the operation period of the device.
(4) Along the material flow direction, the denitrification reaction is gradually reduced, the acid center amount of the catalyst B in the upstream reaction zone is high, the denitrification reaction depth can be effectively increased, and the overall activity of a hydrofining catalyst system is improved.
(3) By adjusting the metal loading amount, the pore diameter, the pore volume and the particle size of each catalyst bed layer hydrofining agent and grading, the stable transition of reactions such as hydrodesulfurization, denitrification, demetalization and the like can be realized, the pressure drop of the reactor and the cold hydrogen amount between bed layers are further reduced, and the economic benefit of enterprises is improved.
Detailed Description
The method of grading a hydrofinishing agent according to the present invention will be further described with reference to the following specific examples. Wherein the acid content of catalyst B, acid content of catalyst L and total acid content of catalyst (B + L) are obtained by pyridine infrared spectrometry, the pore diameter and pore volume of different catalysts are measured by Tristar pore volume and specific surface measuring instrument, and N is adopted 2 Adsorption and desorption. The carbon content in the catalyst was measured by a high temperature combustion method using a Multi EA 2000 carbon sulfur instrument.
TABLE 1 Properties of the stock oils
TABLE 2 reaction conditions
TABLE 3 composition and physicochemical Properties of the catalysts in the comparative examples and examples
The raw oil used in the following examples and comparative examples was Iran VGO, and the properties thereof are shown in Table 1. Taking a typical three-reaction-zone example, the catalyst loading is the same for each reaction zone. The process conditions are the same for all comparative examples and examples as shown in table 2. The catalysts are all laboratory agents, the physicochemical parameters of the catalysts are shown in table 3, and the metal and the carrier contents in the table are the theoretical addition amounts when the catalysts are synthesized.
The preparation of the catalysts referred to in table 3 is as follows:
(1) Adding distilled water into pseudo-boehmite as an aluminum source according to a mass ratio of 1. The average pore diameter was 19.5 nm, and the L acid content was 0.13 mmol/g. Respectively impregnating active metals molybdenum and nickel by using the prepared alumina as a carrier by adopting a two-step isometric impregnation method, roasting the impregnated alumina in a muffle furnace at 450 ℃ to prepare a hydrofining catalyst intermediate, and then adding saturated NH 4 And drying the aqueous solution of F at 120 ℃ for 4 h, and roasting at 450 ℃ to obtain the hydrofining catalyst. Wherein MoO 3 And when the mass fraction of NiO in the catalyst is 9.5 percent and 2.5 percent respectively, the mass fraction of the alumina carrier is 78 percent, and the mass fraction of F is 10 percent, the prepared hydrofining catalyst is A-1. Wherein MoO 3 And NiO in the catalyst respectively account for 14.0 percent and 3.0 percent by mass, the alumina carrier accounts for 74 percent by mass, and the F accounts for 9 percent by mass, and then the prepared hydrofining catalyst is A-2.
(2) Adding distilled water into pseudo-boehmite as an aluminum source according to a mass ratio of 1. The average pore diameter was 16.4 nm, and the acid amount per liter was 0.20 mmol/g. Respectively impregnating active metals molybdenum and nickel by using the prepared alumina as a carrier by adopting a two-step isometric impregnation method, roasting the impregnated alumina in a muffle furnace at 450 ℃ to prepare a hydrofining catalyst intermediate, and then adding saturated NH 4 And drying the aqueous solution of F at 120 ℃ for 4 h, and roasting at 450 ℃ to obtain the hydrofining catalyst. Wherein MoO 3 And NiO in the catalyst respectively account for 18.5 percent and 4.5 percent by mass, the alumina carrier accounts for 69.0 percent by mass, and the F accounts for 8 percent by mass, and then the prepared hydrofining catalyst is B-1. Wherein MoO 3 The mass fractions of the NiO and the alumina carrier in the catalyst are respectively 22.0 percent and 5.0 percentWhen the amount of F was 66.0% and the mass fraction of F was 7%, the hydrorefining catalyst prepared in this case was B-2.
(3) Adding distilled water into pseudo-boehmite serving as an aluminum source according to a mass ratio of 1. The average pore diameter was 10.3 nm, and the L acid amount was 0.32 mmol/g. Respectively impregnating active metals molybdenum and nickel by using the prepared alumina as a carrier by adopting a two-step isometric impregnation method, roasting the impregnated alumina in a muffle furnace at 450 ℃ to prepare a hydrofining catalyst intermediate, and then adding saturated NH 4 And drying the aqueous solution of F at 120 ℃ for 4 h, and roasting at 450 ℃ to obtain the hydrofining catalyst. Wherein MoO 3 When the mass fractions of NiO and NiO in the catalyst were 25.5% and 5.5%, respectively, the mass fraction of the alumina carrier was 63.0%, and the mass fraction of F was 6.0%, the hydrorefining catalyst prepared at this time was C-1. Wherein MoO 3 And NiO in the catalyst respectively account for 29.0 percent and 6.0 percent, the alumina carrier accounts for 60.0 percent, and the F accounts for 5.0 percent, so that the prepared hydrofining catalyst is C-2.
Example 1
The reactor is filled with catalysts A1, B1 and C1 in equal proportion from the front region to the rear region, and raw oil is mixed with hydrogen and then sequentially passes through catalyst beds A1, B1 and C1 in the reactor.
Comparative example 1
The A2 catalyst is filled in the reactor completely, and the raw oil passes through a reactor bed layer after contacting with hydrogen.
Example 2
The reactor is filled with catalysts A1, B2 and C1 in equal proportion from the front region to the rear region, and raw oil is mixed with hydrogen and then sequentially passes through catalyst beds A1, B2 and C1 in the reactor.
Comparative example 2
The reactor is filled with catalyst B2 completely, and the raw oil is contacted with hydrogen and then passes through the bed layer of the reactor.
Example 3
The reactor is filled with catalysts A2, B2 and C2 in equal proportion from the front region to the rear region, and raw oil is mixed with hydrogen and then sequentially passes through catalyst beds A2, B2 and C2 in the reactor.
Comparative example 3
C2 catalyst is filled in the reactor, and the raw oil passes through the bed layer of the reactor after contacting with hydrogen.
The sulfur nitrogen content, removal rate and average carbon deposition per bed of catalyst of all the above comparative examples and examples are shown in Table 4.
The activity evaluation conditions corresponding to the above catalyst grading methods were consistent, as shown in table 2.
TABLE 4 evaluation results of activity and bed deposition amount of comparative examples and examples
The experimental results of the comparative example and the example show that the grading method can improve the desulfurization rate and the denitrification rate and reduce the carbon deposition amount of each bed layer. Comparing example 1 with comparative example 1, it can be seen that, compared with the single hydrofining agent, the carbon deposition amount of all the beds after the grading is less and more uniform, the hydrodesulfurization and denitrification activities are better, and the pressure drop is lower. Comparing example 2 with comparative example 2, it can be seen that when all the refined oils are loaded according to the grading method of this patent, the sulfur content of the refined oils is as low as 5 ppm, the denitrification activity is higher, and the refined nitrogen content is less than 10 ppm. In addition, the total carbon amount of the catalyst bed lamination is minimum, the carbon deposition amount of each bed layer is also minimum, and the pressure drop is minimum. Comparing example 3 with comparative example 3, it can be seen that, although the effect of denitrification and desulfurization is better, the carbon deposition amount of the first bed layer is too high and the pressure drop is the highest by using the single hydrofining catalyst with high metal and high acid content.
Claims (11)
1. A method for grading a hydrofining catalyst comprises the following steps:
after being mixed with hydrogen, the wax oil raw oil passes through a hydrofining reaction zone to be in contact reaction with a hydrofining catalyst, so as to obtain a hydrofining reaction effluent; the hydrofining catalyst takes VIII family and/or VIB family metals as active metal components, alumina as a carrier, and an auxiliary agent fluorine is contained in the catalyst;
the hydrofining reaction zone comprises more than two hydrofining catalyst beds, the active metal component content of the hydrofining catalyst is sequentially increased, the total acid content of the catalyst is sequentially increased, the L acid content is sequentially increased, and the fluorine element content is sequentially reduced according to the contact sequence of the hydrofining catalyst beds and the raw oil;
wherein, in two adjacent hydrofining catalyst beds, the catalyst of the downstream bed is compared with the catalyst of the upstream bed: the fluorine content is reduced by 1.0 to 8.0 percent, the content of active metal components is increased by 3.0 to 20.0 percent in terms of oxide, the total infrared acid content is increased by 0.05 to 0.25 mmol/L, and the L acid content is increased by 0.05 to 0.25 mmol/L;
in the hydrofining catalyst, the content of active metal components in terms of oxide is 10.0-50.0%, the content of fluorine is 1.0-15.0%, the total infrared acid content is 0.05-1.0 mmol/L, and the L acid content is 0.04-0.70 mmol/L based on the weight of the catalyst.
2. The method according to claim 1, wherein the crude oil has a boiling range of 180 to 550 ℃ and a nitrogen content of 1000. Mu.g/g.
3. The process of claim 1 wherein the hydrofinishing reaction zone comprises from 2 to 6 beds of hydrofinishing catalyst.
4. The process of claim 1, wherein in two adjacent beds of hydrofinishing catalyst, the downstream bed catalyst is compared to the upstream bed catalyst by: the fluorine content is 1.5 to 5.0 percent lower, and the content of the active metal component is 5.0 to 15.0 percent higher in terms of oxide.
5. The process according to claim 1, wherein the hydrorefining catalyst has an average pore diameter of 0.5 to 30.0 nm and a pore volume of 0.2 to 1.2 cm 3 The grain diameter is 1.0-30.0 mm.
6. The process of claim 3 wherein the hydrofinishing reaction zone comprises three catalyst beds, the catalyst of the first catalyst bed has a F content of 8.5% to 15.0% and an IR acid content of 0.20 to 0.36 mmol/L; the F content of the second catalyst bed layer hydrogenation catalyst is 6.5-8.4%, and the infrared acid amount is 0.36-0.45 mmol/L; the F content of the third catalyst bed hydrogenation catalyst is 1.0-6.4%, and the infrared acid content is 0.45-0.80 mmol/L.
7. The process according to claim 1 or 6, wherein the average pore diameter of the hydrorefining catalyst is gradually decreased and the particle diameter is gradually decreased in the order of contact with the feedstock oil.
8. The method according to claim 7, wherein the first bed layer hydrofinishing agent has a metal component content of 5.0-18.0 w%, calculated as oxide, an average pore diameter of 14.0-20.0 nm and a particle size of 10.0-20.0 mm; the content of the metal component of the hydrofining agent in the second bed layer is 20.0-28.0 w percent calculated by oxide, the average pore diameter is 10-14 nm, and the particle size is 6-10 mm; the content of the metal component of the hydrofining agent in the third bed layer is 30.0-36.0 w percent calculated by oxide, the average pore diameter is 3.0-6.0 nm, and the particle diameter is 2.0-6.0 mm.
9. The process of claim 1 wherein the process conditions in the hydrofinishing reaction zone comprise: the average reaction temperature is 280-450 ℃, the reaction hydrogen partial pressure is 6-20 MPa, and the hydrogen-oil volume ratio is 300-2000 h -1 The liquid hourly space velocity is 0.1-2 h -1 。
10. The process according to claim 1, wherein the hydrorefining catalyst contains 12.0 to 45.0% of active metal components, calculated as oxides, 2.0 to 10.0% of fluorine, 0.1 to 0.8 mmol/L of total infrared acid, and 0.08 to 0.60 mmol/L of L-acid, based on the weight of the catalyst.
11. The process according to claim 5, wherein the hydrorefining catalyst has an average pore diameter of 4.0 to 20.0 nm and a pore volume of 0.3 to 0.9 cm 3 The grain diameter is 2.0-20.0 mm.
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