CN111849547B - Method for treating light oil of slurry bed - Google Patents
Method for treating light oil of slurry bed Download PDFInfo
- Publication number
- CN111849547B CN111849547B CN201910362043.7A CN201910362043A CN111849547B CN 111849547 B CN111849547 B CN 111849547B CN 201910362043 A CN201910362043 A CN 201910362043A CN 111849547 B CN111849547 B CN 111849547B
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- Prior art keywords
- catalyst
- oxide
- hydrofining
- pore volume
- oil
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 105
- 239000002002 slurry Substances 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 238
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 144
- 239000003921 oil Substances 0.000 claims description 83
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 239000002184 metal Substances 0.000 claims description 52
- 239000002243 precursor Substances 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- 230000009471 action Effects 0.000 description 1
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of oil refining, and discloses a method for treating light oil in a slurry bed. The method comprises the following steps: carrying out a first contact reaction on the slurry bed light oil and hydrogen with a hydrofining catalyst to obtain a hydrofining reaction effluent, then carrying out a second contact reaction on the hydrofining reaction effluent and a hydro-upgrading catalyst to obtain a hydro-upgrading reaction effluent, and fractionating the hydro-upgrading reaction effluent; the light oil in the slurry bed has a distillation range of 50-400 deg.C and a density of 0.80-0.90g/cm3The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%. The invention can obtain products with excellent quality by selecting specific hydrofining catalyst, including naphtha products, aviation kerosene products and diesel oil products.
Description
Technical Field
The invention relates to the technical field of oil refining, in particular to a method for treating light oil in a slurry bed.
Background
With the continuous exploitation and use of petroleum resources, the trend of deterioration and heaviness of petroleum resources is increasing, and how to develop and utilize heavy oil resources is an important topic of petrochemical industry.
CN104560174B discloses a method for heavy oil hydroconversion. The method comprises a hydrocracking system, a hydrocracking system and a hydrotreating system: heavy oil is firstly subjected to a hydro-thermal cracking reaction in a first reactor; separating the reaction product into light distillate oil, heavy distillate oil and residual oil; wherein, the residual oil, the hydrocracking catalyst and the hydrogen enter a second reactor to further carry out hydrocracking reaction; the heavy distillate oil and hydrogen enter a hydrocracking reactor, contact with a hydrocracking catalyst, and undergo a hydrocracking reaction under a hydrocracking condition to obtain light oil; and the light distillate oil and hydrogen enter a hydrofining reactor, contact with a hydrofining catalyst and react to obtain the hydrofined light distillate oil. The method can improve the conversion rate of heavy oil and the yield of light oil, and can obtain gasoline and diesel oil products with excellent performance.
CN103059915B discloses a hydro-upgrading method of inferior heavy oil, which comprises contacting the inferior heavy oil, heavy distillate oil, hydro-upgrading catalyst with hydrogen, wherein the hydro-upgrading catalyst contains 2-15 wt% of metal elements and 85-98 wt% of non-metal elements, more than 95 wt% of the metal elements are V, Ni and lanthanide series metal elements and/or VIB group metal elements; more than 95 weight percent of the nonmetal elements are C and S, at least part of the S and the metal elements exist in the form of sulfides of the metal elements, the heavy fraction oil is the residual part after separating a light fraction from a product obtained by hydro-upgrading of the inferior heavy oil, and the distillation temperature of the light fraction is lower than 500 ℃; the hydro-upgrading method has better hydro-upgrading effect by using the hydro-upgrading catalyst, can improve the conversion rate of raw oil and the yield of light oil, and reduces the yield of coke.
CN107629816A discloses a heavy oil hydrogenation method, which adopts an on-line hydrogenation combined process of a boiling bed and a fixed bed, light oil obtained by hydrogenation of the boiling bed directly enters the fixed bed reactor for hydrogenation reaction without the processes of temperature reduction, pressure reduction and fractionation, thereby avoiding the defect of complex process caused by the conventional off-line hydrogenation combined process that product depressurization separation is carried out first and then pressure rise and temperature rise hydrogenation is carried out, and simultaneously reducing the number of devices in the process flow and reducing energy loss; meanwhile, the method also has the advantages of high light oil yield, low catalyst consumption, reasonable energy utilization and low device energy consumption.
CN103789036B discloses a poor-quality heavy oil combined processing method, which comprises the following steps: a. the heavy oil raw material enters a liquid phase fluidized bed reactor, and is subjected to hydrocracking reaction under the action of hydrogen and a dispersed hydrocracking catalyst; b. fractionating the obtained hydrogenation product to obtain light oil and heavy oil, wherein the cutting point is 320-380 ℃, and the light oil is led out of the device; c. performing solvent extraction on the heavy oil obtained by fractionation to obtain deasphalted oil and deoiled asphalt; d. wherein the deasphalted oil is contacted with a catalytic cracking catalyst, the cracking reaction is carried out under the catalytic cracking condition, and light oil, heavy cycle oil and oil slurry are obtained by fractionation; e. and (c) recycling the deoiled asphalt obtained in the step (c) to the liquid phase flow bed reactor in the step (a). The method integrates various processes to treat the inferior heavy oil, not only can realize the full conversion of the heavy oil, but also can obtain more gasoline and diesel oil with excellent performance.
The slurry bed process technology can convert inferior residual oil and heavy oil into naphtha, diesel oil and wax oil, and improves the utilization rate of resources. However, the properties of the distillate products produced by the slurry bed technology are inferior, and further processing is needed to obtain qualified products. In the prior art, diesel oil is produced by treating light oil in a slurry bed through a hydrofining technology, but the naphtha fraction and the diesel oil fraction in the slurry bed have high sulfur and nitrogen contents, most of sulfides and nitrides in the naphtha fraction and the diesel oil fraction are macromolecular low-activity compounds, so that the removal difficulty is high, the reaction conditions are severe, and the diesel oil product cannot meet the clean diesel oil standard of China VI and can only be used as a blending component of the diesel oil.
Disclosure of Invention
The object of the present invention is to overcome the problems of the prior art and to provide a method for treating a light oil in a slurry bed, which method makes it possible to make reasonable use of the light oil in a slurry bed and to obtain a product of good quality.
In order to achieve the above object, the present invention provides a method of treating slurry bed light oil, the method comprising:carrying out a first contact reaction on the slurry bed light oil and hydrogen with a hydrofining catalyst to obtain a hydrofining reaction effluent, then carrying out a second contact reaction on the hydrofining reaction effluent and a hydro-upgrading catalyst to obtain a hydro-upgrading reaction effluent, and fractionating the hydro-upgrading reaction effluent; the light oil in the slurry bed has a distillation range of 50-400 deg.C and a density of 0.80-0.90g/cm3The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%;
wherein the hydrofining catalyst contains an inorganic refractory component, a hydrodesulfurization catalytic active component, alcohol and carboxylic acid;
the inorganic refractory component contains at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and part of hydrodesulfurization catalytic active component;
the hydrofining catalyst has a pore diameter of 2-40nm and a pore diameter of 100-300nm, wherein the pore volume of the pore diameter of 2-40nm accounts for 60-95% of the total pore volume, and the pore volume of 100-300nm accounts for 0.5-30% of the total pore volume.
Compared with the prior art, the method provided by the invention can obtain products with excellent quality, wherein the sulfur content of the obtained naphtha product is less than 0.5 mu g/g, the nitrogen content is less than 0.5 mu g/g, and the naphtha product can be used as a raw material of a high-quality reforming device; the aviation kerosene product meets the No. 3 jet fuel standard GB 6537-2006; the diesel oil product meets the national VI standard GB 19147-2016.
Drawings
FIG. 1 is a schematic process flow diagram according to a preferred embodiment of the present invention;
FIG. 2 is a schematic process flow diagram according to another preferred embodiment of the present invention.
Description of the reference numerals
1-slurry bed light oil 2-hydrofining reaction zone
3-hydrogenation modification reaction zone 4-heat exchanger
5-high pressure separator 6-recycle hydrogen desulfurization system
7-recycle hydrogen compressor 8-low pressure separator
9-fractionation System 10-overhead gas
11-naphtha product 12-diesel product
13-aviation kerosene product 14-cycle hydrogen
15-fresh hydrogen 16-heating furnace
17-partial diesel products
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for treating light oil in a slurry bed, which comprises the following steps: and carrying out a first contact reaction on the slurry bed light oil and hydrogen with a hydrofining catalyst to obtain a hydrofining reaction effluent, then carrying out a second contact reaction on the hydrofining reaction effluent and a hydro-upgrading catalyst to obtain a hydro-upgrading reaction effluent, and fractionating the hydro-upgrading reaction effluent.
In the present invention, the slurry bed light oil refers to light oil fractions having an end point of 400 ℃ or lower obtained by subjecting a liquid product obtained in a slurry bed unit to atmospheric and vacuum fractionation, and includes naphtha fractions and diesel fractions. The raw materials of the slurry state unit can be heavy materials such as atmospheric residue, vacuum residue, coal tar, direct coal liquefaction oil, ethylene tar, shale oil, heavy oil, biomass heavy oil and the like. The processing of the slurry bed unit may be carried out according to the method in CN103059915B or CN104560170B, but the present invention is not limited to this method. The light oil in the slurry bed has a distillation range of 50-400 deg.C and a density of 0.80-0.90g/cm3The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%. In the present invention, the distillation range is measured by the method ofASTM D-86。
The research finds that the slurry bed light oil has the following characteristics: (1) the nitrogen content is ultrahigh and is as high as more than 1000 mug/g, most of light oil exceeds 2500 mug/g, which is obviously different from the knowledge and processing experience of common diesel oil fraction, and the reference experience is few; (2) the heteroatom content such as sulfur and nitrogen is high, and the molecular reactivity such as sulfur, nitride and the like with steric hindrance is low; (3) the nitrogen content of naphtha fraction in light oil is ultrahigh, and the conventional low-pressure reforming pre-hydrogenation device is difficult to treat; (4) the diesel oil fraction in the light oil has high density, high aromatic hydrocarbon content and low cetane number.
According to the conventional diesel hydrodenitrogenation reaction law: firstly, high-content organic nitrogen molecules in diesel oil compete and are adsorbed on an active center of a catalyst, so that ultra-deep desulfurization (HDS) reaction and hydrogenation saturation reaction of aromatic hydrocarbon are inhibited; secondly, under the condition of lower hydrogen partial pressure, nitrides can be adsorbed on the acid center on the surface of the catalyst, the carbon deposition and inactivation of the catalyst are accelerated, the reaction activity of hydrodesulfurization and hydrodenitrogenation is reduced, and the running period is shortened; thirdly, the inorganic ammonia generated after ultra-deep denitrification can seriously inhibit the exertion of the activity of the upgrading catalyst and reduce the improvement range of the cetane number.
In the present invention, the hydrogen may be recycled hydrogen separated from the hydroupgrading reaction effluent and/or make-up fresh hydrogen.
In the present invention, the hydrofining catalyst contains an inorganic refractory component, a hydrodesulfurization catalytic active component, an alcohol and a carboxylic acid; the inorganic refractory component contains at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and part of hydrodesulfurization catalytic active component; the hydrofining catalyst has a pore diameter of 2-40nm and a pore diameter of 100-300nm, wherein the pore volume of the pore diameter of 2-40nm accounts for 60-95% of the total pore volume, and the pore volume of 100-300nm accounts for 0.5-30% of the total pore volume.
The inventors of the present invention have found that introduction of an alcohol, preferably an organic alcohol compound, into a hydrorefining catalyst can effectively protect active components in the catalyst, and introduction of a carboxylic acid compound into the hydrorefining catalyst can improve the activity of the catalyst, and can also exert a synergistic effect when both are present. Therefore, it is possible to protect the catalyst active component and to improve the catalyst activity by introducing an alcohol and a carboxylic acid into the catalyst, the mole number of the alcohol being in a weight ratio of 0.005 to 0.03 on a dry basis of the inorganic refractory component: 1, preferably 0.01 to 0.02: 1; the weight ratio of the carboxylic acid to the inorganic refractory component on a dry basis is from 0.002 to 0.1, preferably from 0.02 to 0.06.
Preferably, the alcohol is selected from at least one of C1-18 monohydric alcohols, preferably C1-10 monohydric alcohols (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 monohydric alcohols) (such as but not limited to methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol), ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, and trimethylolethane.
Preferably, the carboxylic acid is selected from at least one of C1-18 monobasic saturated carboxylic acids (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 monobasic saturated carboxylic acids) (e.g., but not limited to, formic acid, acetic acid, propionic acid, octanoic acid, valeric acid, hexanoic acid, decanoic acid, pentanoic acid), C7-10 phenyl acids (e.g., C7, C8, C9, C10 phenyl acids) (e.g., but not limited to, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid), citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and the like.
According to a preferred embodiment of the present invention, in order to further improve the performance of the hydrorefining catalyst, the hydrorefining catalyst further contains a phosphorus element, preferably P2O5Exist in the form of (1). Preferably, P is the amount of the hydrorefining catalyst on a dry weight basis2O5The content of the phosphorus element is 0.8 to 10% by weight, more preferably 1 to 8% by weight.
According to the present invention, preferably, the hydrofining catalyst is a shaped catalyst, and the shape of the hydrofining catalyst is preferably a cylinder, a clover or a honeycomb.
The pore channel structures of the hydrofining catalyst used in the invention are respectively concentrated between 2-40nm and 100-300 nm. The pore passage of 100-300nm in the hydrofining catalyst can provide enough places for the diffusion of reactants, and promotes the accessibility of the reactants and the active center, thereby improving the performance of the catalyst. The hydrofining catalyst has high hydrodesulfurization activity, hydrodenitrogenation performance and aromatic hydrocarbon saturation performance, and provides a proper feeding material for a hydrogenation modification reaction zone.
In the course of research, the inventors of the present invention found that the carrier of the hydrorefining catalyst is usually obtained by extruding a carrier precursor (such as pseudo-boehmite powder) with a peptizing agent and an extrusion aid to form a strip, and then drying and calcining the strip. Since the hydrorefining reaction requires a catalyst with a larger pore structure, and before calcination, the pores are generally concentrated at 2-12nm, so that the pore size of the catalyst is generally increased by calcining the molded carrier to increase the pore size of the carrier, the pores of the calcined carrier are generally concentrated at 2-100nm, the average pore size of the carrier is increased, and it is generally considered that the pore size is larger as the calcination temperature is higher. However, the inventors of the present invention found in their studies that collapse condensation occurs in the pore walls of the carrier with an increase in the calcination temperature. Although pore wall condensation may increase the average pore size of the support, the condensed pore walls may reduce the utilization of alumina, thereby reducing the catalytic activity of the catalyst. According to the preparation method of the hydrofining catalyst, the precursor of the carrier is preferably roasted before extrusion molding, so that on one hand, the number of hydroxyl groups in the precursor particles of the carrier can be reduced through heat treatment, the probability of channel condensation is reduced, and the aperture of the hydrofining catalyst is increased. In the second aspect, the formed hydrofining catalyst does not need to be processed at a higher temperature, and the pore wall of the carrier does not need to be subjected to excessive condensation, so that the utilization rate of the carrier is improved. In the third aspect, the carrier precursor is subjected to heat treatment before molding, and partial secondary particles are also condensed, so that the size of the formed alumina particles tends to be single, and the pore channels in the molded hydrofining catalyst are more uniform, which is beneficial to the diffusion of reactants. Especially for heavier and inferior oil products, the catalyst is more effective than the conventional hydrofining catalyst.
The inventor of the present invention has found that the hydrofining catalyst prepared by the conventional impregnation method has a low metal loading, the content of the group VIII metal is usually less than 10%, and the content of the group VIB metal is usually less than 35%. This limits the number of active metal sites of the hydrofinishing catalyst, which do not reach higher levels of activity. The hydrofining catalyst prepared by the kneading method can improve the loading capacity of active metal in the hydrofining catalyst, but the hydrofining activity of the catalyst is not high, and the utilization rate of the active metal is low. Currently, hydrofinishing catalysts are generally not prepared by this method. In the present invention, a portion of the hydrodesulfurization catalytically active component, and more preferably a portion of the group VIII metal, is mixed into a support precursor and calcined to form the inorganic refractory powder. And then mixing the impregnation liquid containing the residual active metal with the inorganic refractory powder, thereby improving the content of the active components in the hydrofining catalyst and further improving the hydrofining performance of the catalyst.
In a preferred aspect, the hydrofinishing catalyst of the present invention comprises an inorganic refractory component containing at least one of silica, magnesia, calcia, zirconia and titania and a part of the group VIII metal element, a group VIB metal element, an organic acid and an alcohol, wherein the content of the inorganic refractory component is not more than 40%.
The hydrorefining catalyst of the present invention may contain no pore-expanding agent such as carbon black, graphite, stearic acid, sodium stearate, or aluminum stearate, or may contain no component such as a surfactant, and may directly satisfy the demand for reactivity.
The silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide contained in the inorganic refractory component are basically inert substances and are difficult to combine with the VIII family element to form a compound with a stable structure, so that the utilization rate of the VIII family element is improved. In addition, the inorganic refractory components have weak acting force with other active components of the hydrofining catalyst, so that the growth of an active phase of the hydrofining catalyst can be promoted, and the performance of the hydrofining catalyst is further promoted.
Preferably, the pore volume of pores with a pore diameter of 2-40nm accounts for 75-90% of the total pore volume, and the pore volume of pores with a pore diameter of 100-300nm accounts for 5-15% of the total pore volume. Wherein the pore volume of pores with a diameter of 2-4nm is not more than 10% of the total pore volume.
According to the invention, the specific surface area of the hydrofining catalyst and the pore distribution, the pore diameter and the pore volume of 2-40nm are measured by a low-temperature nitrogen adsorption method (meeting the GB/T5816-1995 standard), and the pore distribution, the pore diameter and the pore volume of 100-300nm are measured by a mercury intrusion method. The pore volume of the hydrorefining catalyst with the pore diameter less than 100nm is measured by a low-temperature nitrogen adsorption method, the pore volume of the hydrorefining catalyst with the pore diameter more than 100nm is measured by a mercury intrusion method, and the pore volume of the hydrorefining catalyst is the sum of the pore volume and the pore volume. The average pore diameter was calculated according to the cylindrical pore model (average pore diameter ═ total pore volume × 4000/specific surface area).
Preferably, the specific surface area of the hydrofining catalyst is 70-200m2A/g, preferably from 90 to 180m2Pore volume of 0.15 to 0.6mL/g, preferably 0.2 to 0.4mL/g, and average pore diameter of 5 to 25nm, preferably 8 to 15 nm. The specific surface area, the pore volume and the average pore diameter are measured after the hydrofining catalyst is calcined at 400 ℃ for 3 hours.
According to the invention, the pore diameter of 2-40nm means a pore diameter of 2nm or more and less than 40nm, and the pore diameter of 100-300nm means a pore diameter of 100nm or more and less than 300nm, unless otherwise stated. The average pore diameter of 5 to 25nm means that the average of the pore diameters of all pores of the hydrorefining catalyst is not less than 5nm and not more than 25 nm. The pore diameter of 2-4nm is larger than or equal to 2nm and smaller than 4 nm.
According to the invention, the hydrodesulphurization catalytically active component may be a component of an active component that is currently available for hydrofinishing catalysts, for example, the active component may comprise elements of group VIII metals and elements of group VIB metals. Wherein the content of the active component may also vary within wide limits, it is preferred that the content of group VIII metal elements in the hydrofinishing catalyst is from 15 to 35 wt.%, preferably from 20 to 30 wt.%, based on the dry weight of the catalyst and calculated as oxide; the content of group VIB metal elements is from 35 to 75% by weight, preferably from 40 to 65% by weight.
According to a preferred embodiment of the present invention, the group VIII metal element is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, and the group VIB metal element is selected from at least one of chromium, molybdenum and tungsten.
The inventors of the present invention have found in their studies that, by preferably including a part of the group VIII metal element in the inorganic refractory component, the content of the active component in the hydrorefining catalyst can be further increased, thereby further improving the hydrorefining performance of the catalyst. The amount ratio of the group VIII metal element contained in the inorganic refractory component is not particularly limited and may be selected from a wide range, and preferably, the content of the partial group VIII metal element is 60 to 90% of the total content of the group VIII metal elements.
According to the present invention, the inorganic refractory component is preferably contained in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight, based on the dry weight of the hydrofinishing catalyst.
Here, the dry weight of the inorganic refractory powder is a weight measured by calcining a sample at 600 ℃ for 4 hours, and the dry weight of the hydrorefining catalyst is a weight measured by calcining a sample at 400 ℃ for 3 hours. The dry basis weights appearing hereinafter are equally applicable to this definition. That is, in the case where there is no reverse explanation, the dry weight of the inorganic refractory powder as described herein means the weight determined by calcining a sample at 600 ℃ for 4 hours, and the dry weight of the hydrofinishing catalyst is determined by calcining a sample at 400 ℃ for 3 hours. It will be appreciated by those skilled in the art that the alcohol and organic acid contained in the hydrofinishing catalyst will decompose and volatilize at high temperatures when calculated on a dry weight basis, and therefore the alcohol and organic acid content is not calculated on a dry weight basis.
In the present invention, the above-mentioned hydrorefining catalyst can be prepared by the following method:
(1) mixing and roasting a precursor containing at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and a precursor of a part of hydrodesulfurization catalytic active component to obtain an inorganic refractory component;
(2) mixing alcohol, carboxylic acid and the precursor of the residual hydrodesulfurization catalytic active component to obtain impregnation liquid;
(3) and mixing the inorganic refractory component with the impregnation liquid, and molding and drying the obtained mixture to obtain the hydrofining catalyst.
According to the invention, the precursors of the hydrodesulfurization catalytic active components are preferably precursors of group VIII metal elements and of group VIB metal elements; the precursors of the VIII group metal elements and the VIB group metal elements are used in amounts which are based on the dry weight of the catalyst and calculated by oxides, the contents of the VIII group metal elements and the VIB group metal elements are respectively the contents described in the above, and the selection of the specific elements is also performed as described in the above.
According to the present invention, in the precursor of the hydrodesulfurization catalytic active component, the precursor of the iron element may include, but is not limited to, one or more of iron nitrate, iron oxide, basic iron carbonate and iron acetate, the precursor of the cobalt element may include, but is not limited to, one or more of cobalt nitrate, basic cobalt carbonate, cobalt acetate and cobalt oxide, the precursor of the nickel element may include, but is not limited to, one or more of nickel nitrate, basic nickel carbonate, nickel acetate and nickel oxide, the precursor of the ruthenium element may include, but is not limited to, one or more of ruthenium nitrate, ruthenium acetate, ruthenium oxide and ruthenium hydroxide, the precursor of the rhodium element may include, but is not limited to, one or more of rhodium nitrate, rhodium hydroxide and rhodium oxide, and the precursor of the palladium element may include, but is not limited to, one or more of palladium nitrate, palladium oxide and palladium hydroxide, the precursors of the chromium element can include but are not limited to one or more of chromium nitrate, chromium oxide, chromium hydroxide and chromium acetate, the precursors of the molybdenum element can include but is not limited to one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate and molybdenum oxide, and the precursors of the tungsten element can include but is not limited to one or more of ammonium metatungstate, ammonium ethylmetatungstate and tungsten oxide.
The inventor of the present invention found in research that, preferably, by preparing a part of the precursor of the group VIII metal element into the inorganic refractory component and preparing an impregnation solution by using the rest of the precursor of the group VIII metal element and the precursor of the group VIB metal element together to impregnate the inorganic refractory component, the content of the active component in the hydrorefining catalyst can be further increased, thereby further improving the hydrorefining performance of the catalyst. While the amount ratio of the precursor of the group VIII metal element used for preparing the inorganic refractory component is not particularly limited and may be selected from a wide range, it is preferable that the amount of the partial precursor of the group VIII metal element is 60 to 90% of the total amount of the precursor of the group VIII metal element in step (1).
According to the invention, in the step (1), the precursor of silica, magnesia, calcia, zirconia, titania can be various substances which can provide silica, magnesia, calcia, zirconia, titania under the roasting condition, for example, the silica precursor can be silica sol, silica white, silica dioxide, etc.; the magnesium oxide precursor is magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium oxide and the like; the precursor of the calcium oxide is calcium hydroxide, calcium carbonate, calcium oxalate, calcium nitrate, calcium acetate, calcium oxide and the like; the zirconia precursor is zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium acetate, zirconia and the like; the precursor of the titanium oxide is titanium hydroxide, titanium nitrate, titanium acetate, zirconium oxide and the like.
In step (3), the inorganic refractory component is used in an amount such that the content of the inorganic refractory component in the hydrofinishing catalyst is 5 to 40% by weight, preferably 10 to 30% by weight, based on the dry weight of the hydrofinishing catalyst.
In step (2), the amounts and selection of the alcohol and the carboxylic acid have been described in detail above, and will not be repeated here.
According to the invention, the alcohol and the carboxylic acid substances are introduced into the impregnation liquid, so that the hydrodesulfurization catalytic active component can be effectively protected, and the catalyst can be promoted to be molded, thereby effectively improving the performance of the catalyst.
In order to further improve the performance of the finally prepared catalyst, the average pore diameters of the silicon oxide, the magnesium oxide, the calcium oxide, the zirconium oxide and the titanium oxide precursors are not less than 10nm, the pore volume of the pore diameters of 2-6nm accounts for no more than 15% of the total pore volume, and the pore volume of the pore diameters of 6-40nm accounts for no less than 75% of the total pore volume.
According to the present invention, in order to further improve the solubility of the precursor of the hydrodesulfurization catalytic active component in the prepared impregnation solution and improve the performance of the finally prepared hydrofining catalyst, a phosphorus-containing substance is preferably added during the preparation of the impregnation solution, and the phosphorus-containing substance is preferably a phosphorus-containing inorganic acid, and is further preferably at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate. Further preferably, the phosphorus-containing material is used in an amount such that the final hydrofinishing catalyst is prepared on a dry weight basis and in terms of P2O5The content of the phosphorus element is 0.8 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 8% by weight.
According to a preferred embodiment of the invention, in the process of preparing the impregnating solution, the alcohol compound and the precursor respectively containing the VIB group metal element and the VIII group metal element are firstly added into the aqueous solution of the phosphorus-containing substance, and then stirred for 1-8 hours at 40-100 ℃ until the alcohol compound and the precursor are completely dissolved. Finally, the organic acid is added until the organic acid is completely dissolved. The order of addition of the organic alcohol compound, the organic carboxylic acid compound, the phosphorus-containing substance, and the metal element precursor may be changed.
According to the invention, in the step (1), the roasting conditions can be selected within a wide range, and preferably, the roasting temperature is 300-900 ℃, preferably 400-700 ℃; the roasting time is 1-15h, preferably 3-8 h.
According to the present invention, in the step (3), the drying conditions can be selected within a wide range, and preferably, the drying temperature is 50-250 ℃, preferably 100-200 ℃; the drying time is 2-10h, preferably 3-8 h.
According to the invention, the forming mode can be various existing forming methods, such as extrusion molding and rolling ball molding. The extrusion molding can be performed according to the prior art, and the inorganic refractory component to be extruded and molded and the impregnation solution containing the metal component are uniformly mixed and then extruded into a required shape, such as a cylinder, a clover shape, a honeycomb shape and the like.
In the invention, the effluent of the hydrofining reaction is directly subjected to a second contact reaction with a hydrofining catalyst without separation, wherein the hydrofining catalyst can be obtained commercially. According to the invention, the hydrogenation modification catalyst has excellent aromatic saturation and selective ring-opening performance, and can greatly improve the cetane number and aviation kerosene cut smoke point of inferior diesel oil. Furthermore, the hydrogenation modification catalyst has excellent organic nitrogen and inorganic ammonia resistance, and can still have excellent selective ring opening performance of naphthenic hydrocarbon and naphthenic aromatic hydrocarbon in an inorganic ammonia atmosphere with a certain concentration.
Preferably, the hydro-upgrading catalyst comprises a carrier and a metal component supported on the carrier; the carrier contains amorphous silicon-aluminum and a molecular sieve; the amorphous silicon-aluminum comprises aluminum oxide and silicon oxide-aluminum oxide with a pseudo-boehmite structure; the molecular sieve is selected from at least one of faujasite, mordenite, L-type zeolite, omega zeolite, Y-type zeolite and Beta zeolite; the metal component is VIB group metal element and VIII group metal element, preferably at least one of Mo, W, Co and Ni.
Preferably, the content of the alumina-silica is 1-70 wt%, the content of the molecular sieve is 1-60 wt%, and the content of the alumina is 5-80 wt% based on the total amount of the hydro-upgrading catalyst; calculated by oxide, the content of VIII group metal elements is 1-15 wt%, and the content of VIB group metal elements is 10-40 wt%.
In the present invention, the hydrofining catalyst is sulfided before use, and the sulfiding conditions of the hydrofining catalyst may be the conditions used for sulfiding the hydrofining catalyst, and the sulfiding method is not particularly limited, and may be dry sulfiding or wet sulfiding.
In the invention, the hydrogenation modification catalyst can be a hydrogenation modification catalyst which is purchased from ChangLing Branch of China petrochemical engineering Limited and has the product brands of RIC-3 and RHC-210.
In the invention, the volume ratio of the dosage of the hydrofining catalyst to the dosage of the hydro-upgrading catalyst is 1 (1-4).
According to the present invention, preferably, the conditions under which the first contact reaction is carried out include: the hydrogen partial pressure is 8.0-14.0MPa, preferably 8.5-14.0 MPa; the temperature is 300-450 ℃, preferably 350-430 ℃; the volume ratio of the hydrogen to the oil is 500-1500, preferably 600-1200; the liquid hourly space velocity is 0.5-4.0h-1Preferably 0.5 to 2.0h-1。
According to the present invention, preferably, the conditions under which the second contact reaction is carried out include: the hydrogen partial pressure is 8.0-14.0MPa, preferably 8.3-13.8 MPa; the temperature is 300-450 ℃, and the temperature is preferably 370-430 ℃; the volume ratio of the hydrogen to the oil is 500-1500, preferably 600-1200; the liquid hourly space velocity is 0.5-4.0h-1Preferably 0.5-2.5h-1。
According to a preferred embodiment of the present invention, the slurry bed light oil and the hydrogen gas undergo a first contact reaction with the hydrofining catalyst in the hydrofining reaction zone, and a hydrogenation protecting agent is further packed upstream of the hydrofining catalyst in the hydrofining zone to prevent the hydrofining catalyst from coking by coking precursors such as olefins and gums in the slurry bed light oil and to protect the hydrofining catalyst. Preferably, the loading of the hydrogenation protection is 5-30 vol% based on the total amount of the hydrogenation protection agent and the hydrofining catalyst. The hydrogenation protective agent can be obtained commercially, and can be a hydrogenation protective agent with a commercial product number RG-30A, RG-30B from Changjingtai, China petrochemical engineering, Inc. Preferably, the hydrogenation protective agent contains 1.0-5.0 wt% of nickel oxide, 5.5-10.0 wt% of molybdenum oxide and 85-93.5 wt% of alumina carrier with double pore distribution.
According to another preferred embodiment of the present invention, the effluent of the hydrorefining reaction is subjected to a second contact with a hydrorefining catalyst in a hydrorefining reaction zone, and a post-refining catalyst is further filled in the hydrorefining reaction zone downstream of the hydrorefining catalyst, so as to further reduce the content of olefins and mercaptan sulfur in the reaction product. The additional refining catalyst is the hydrorefining catalyst of the present invention described above, and may be selected within the range defined by the present invention. Preferably, the loading of the post-purification catalyst is 10 to 50 vol% based on the total amount of the hydro-upgrading catalyst and the post-purification catalyst.
In the present invention, the method for fractionating the effluent of the hydroupgrading reaction may be a method commonly used in the art as long as the desired product can be obtained, and the present invention is not particularly limited thereto.
Several preferred embodiments are provided below:
firstly, as shown in figure 1, slurry bed light oil 1, circulating hydrogen 14 and fresh hydrogen 15 are mixed, then pass through a heat exchanger 4 and a heating furnace 16, enter a hydrofining reaction zone 2 and perform a first contact reaction with a hydrofining catalyst, the obtained hydrofining reaction effluent directly enters a hydro-upgrading reaction zone 3 without being separated and performs a second contact reaction with the hydro-upgrading catalyst, the obtained hydro-upgrading reaction effluent is cooled by the heat exchanger 4 and then enters a high-pressure separator 5, and hydrogen-rich gas, liquid-phase components and acidic water are separated; the hydrogen-rich gas enters a recycle hydrogen desulfurization system 6, hydrogen sulfide is removed, and then the hydrogen-rich gas enters a recycle hydrogen compressor 7 to be recycled to obtain recycle hydrogen 14; the liquid phase component enters a low-pressure separator 8 to separate low-fraction gas and low-fraction oil, the low-fraction oil enters a fractionation system 9 to separate tower top gas 10, naphtha product 11, aviation kerosene product 13 and diesel oil product 12.
(II) as shown in figure 2, after mixing the slurry bed light oil 1, the circulating hydrogen 14 and the fresh hydrogen 15, passing through a heat exchanger 4 and a heating furnace 16, entering a hydrofining reaction zone 2 to perform a first contact reaction with a hydrofining catalyst, directly entering a hydrofining reaction effluent into a hydro-upgrading reaction zone 3 without separation to perform a second contact reaction with the hydro-upgrading catalyst, cooling the obtained hydro-upgrading reaction effluent through the heat exchanger 4, and then entering a high-pressure separator 5 to separate out a hydrogen-rich gas, a liquid-phase component and acidic water; the hydrogen-rich gas enters a recycle hydrogen desulfurization system 6, hydrogen sulfide is removed, and then the hydrogen-rich gas enters a recycle hydrogen compressor 7 to be recycled to obtain recycle hydrogen 14; the liquid phase component enters a low-pressure separator 8 to separate low-fraction gas and low-fraction oil, the low-fraction oil enters a fractionation system 9 to separate tower top gas 10, naphtha product 11, aviation kerosene product 13 and diesel oil product 12; wherein, part of the diesel oil product 17 in the diesel oil product 12 is used as cycle diesel oil to be mixed with the slurry bed light oil 1 and then enters the hydrofining reaction zone 2, and the rest can be used as an ethylene cracking raw material or a clean diesel oil blending component with high cetane number.
The present invention will be described in detail below by way of examples.
In the following preparation examples, the composition of the catalyst was calculated from the amounts charged. The mass fractions of sulfur and nitrogen in the product were analyzed using a sulfur-nitrogen analyzer (model number TN/TS3000, available from seimer feishei), and the content of aromatic hydrocarbons was analyzed by near infrared spectroscopy. The specific surface area of the catalyst and the pore distribution, the pore diameter and the pore volume of the catalyst between 2 and 40nm are measured by a low-temperature nitrogen adsorption method (meeting the GB/T5816-1995 standard), and the pore distribution, the pore diameter and the pore volume of the catalyst between 100 and 300nm are measured by a mercury intrusion method. The average pore diameter of the catalyst was calculated according to the cylindrical pore model (average pore diameter ═ total pore volume × 4000/specific surface area).
In the following examples and comparative examples, the hydrorefining catalyst RN-410, the hydroupgrading catalyst RIC-3, the hydroupgrading catalyst RHC-210, the hydrogenation protecting agent RG-30A and the hydrogenation protecting agent RG-30B were obtained from ChangLing division, petrochemical Co., Ltd, China. The catalyst needs to be presulfided before use, and the presulfiding process is a conventional industrial sulfurization method well known in the field.
The properties of the raw slurry bed light oil a, slurry bed light oil B and slurry bed light oil C are shown in table 1.
The yield of each product fraction is defined as the weight percentage of each product to the feedstock obtained by fractional distillation.
TABLE 1
Preparation example 1
(1) Commercially available white carbon black (specific surface area: 220 m)2The average pore diameter is 12.7nm), and basic nickel carbonate powder are evenly mixed and then roasted for 4h at 700 ℃ to obtain the nickel-containing inorganic refractory powder.
Wherein the amount of basic nickel carbonate used corresponds to a nickel content (calculated as nickel oxide) of 15.0 wt.% in the catalyst.
(2) Adding a certain amount of MoO3Adding basic nickel carbonate and ethylene glycol into the aqueous solution containing phosphoric acid respectively, heating and stirring until the basic nickel carbonate and the ethylene glycol are completely dissolved, and then adding a certain amount of acetic acid until the acetic acid is completely dissolved to obtain the impregnation solution containing the active metal.
Wherein the mass ratio of the mole number of the ethylene glycol to the inorganic refractory component is 0.015, and the mass of the acetic acid is 3 wt% of the mass of the inorganic refractory component.
(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst was dried at 200 ℃ for 5h to obtain an oxidized catalyst with a particle size of 1.6mm, which was designated as hydrofinishing catalyst Z-1.
Wherein the impregnating solution and the nickel-containing inorganic refractory powder are mixed in such a proportion that the content of molybdenum oxide, the content of nickel oxide and the content of P in the catalyst are 46.0 wt%, 20.0 wt% and 20.0 wt%, respectively, based on the dry weight of the catalyst and calculated as an oxide2O5The content was 4% by weight, and the content of the inorganic refractory component was 30.0% by weight.
After the hydrofining catalyst Z-1 is roasted for 3h at 400 ℃, the pore size distribution of the hydrofining catalyst is analyzed by utilizing low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-1 is 145m2The pore diameter is distributed between 2-40nm and 100-300nm, wherein the proportion of the pore volume of 2-40nm to the total pore volume is85.5% (wherein the pore volume at 2-4nm accounted for 7.6% of the total pore volume), 100-300nm accounted for 13.2% of the total pore volume, 0.36mL/g of the pore volume, and 9.9nm of the average pore diameter.
Preparation example 2
(1) Commercially available white carbon black (specific surface area: 220 m)2The average pore diameter is 12.7nm), and basic nickel carbonate powder are evenly mixed and then roasted for 8 hours at the temperature of 600 ℃ to obtain the nickel-containing inorganic refractory powder.
The amount of basic nickel carbonate used corresponds to a nickel content (calculated as nickel oxide) of 27.0% by weight of the catalyst.
(2) Adding a certain amount of MoO3Respectively adding ammonium metatungstate, basic nickel carbonate and ethylene glycol into a water solution containing phosphoric acid, heating and stirring until the ammonium metatungstate, the basic nickel carbonate and the ethylene glycol are completely dissolved, and then adding a certain amount of acetic acid until the acetic acid is completely dissolved to obtain an impregnation solution containing active metals.
Wherein the mass ratio of the mole number of the ethylene glycol to the inorganic refractory component is 0.012, and the mass of the acetic acid is 6 wt% of the mass of the inorganic refractory component.
(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst was dried at 300 ℃ for 3h to obtain an oxidized catalyst with a particle size of 1.6mm, which was designated as hydrofinishing catalyst Z-2.
Wherein the mixing ratio of the impregnating solution and the nickel-containing inorganic refractory powder is such that the content of molybdenum oxide in the catalyst is 22.5 wt%, the content of tungsten oxide is 22.5 wt%, the content of nickel oxide is 27.0 wt%, and P is calculated by oxide based on the dry weight of the catalyst2O5The content was 4.0% by weight, and the content of the inorganic refractory component was 15.0% by weight.
And roasting the hydrofining catalyst Z-2 at 400 ℃ for 3 hours, and analyzing the pore size distribution of the hydrofining catalyst by using a low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-2 is 120m2A pore size distribution of 2 to 40nm and 100-300nm, wherein the proportion of the pore volume of 2 to 40nm to the total pore volume is 76.9% (wherein the proportion of the pore volume of 2 to 4nm to the total pore volume is 9.5%), and the proportion of the pore volume of 100-300nm to the total pore volume isThe volume fraction was 20.3%, the pore volume was 0.26mL/g, and the average pore diameter was 8.7 nm.
Preparation example 3
(1) Commercially available white carbon black (specific surface area: 220 m)2The average pore diameter is 12.7nm), magnesium nitrate and basic nickel carbonate powder are evenly mixed and then roasted for 3h at 400 ℃ to obtain the inorganic refractory powder containing nickel, silicon dioxide and magnesium oxide.
Wherein the amount of basic nickel carbonate used corresponds to 21.0 wt.% of the nickel content (calculated as nickel oxide) in the catalyst.
(2) Respectively adding a certain amount of ammonium metatungstate, nickel nitrate and glycerol into the aqueous solution, heating and stirring until the ammonium metatungstate, the nickel nitrate and the glycerol are completely dissolved, and then adding a certain amount of citric acid until the citric acid is completely dissolved to obtain an impregnation solution containing active metals.
Wherein the mass ratio of the mole number of the glycerol to the inorganic fire-resistant component is 0.008, and the mass of the citric acid is 8 wt% of the mass of the inorganic fire-resistant component.
(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst is dried for 5h at 180 ℃ to obtain an oxidation state catalyst with the particle size of 1.6mm, which is marked as a hydrofining catalyst Z-3.
Wherein the impregnation solution and the nickel-containing inorganic refractory powder are mixed in such proportions that the content of tungsten oxide, the content of nickel oxide, the content of silica and the content of magnesium oxide in the catalyst are 53.0 wt%, 25.0 wt%, 15 wt% and 7.0 wt%, respectively, based on the dry weight of the catalyst and in terms of oxides.
And roasting the hydrofining catalyst Z-3 at 400 ℃ for 3 hours, and analyzing the pore size distribution of the hydrofining catalyst by using a low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-3 is 165m2(ii)/g, the pore diameter distribution was 2 to 40nm and 100-300nm, wherein the ratio of the pore volume of 2 to 40nm to the total pore volume was 87.5% (wherein the ratio of the pore volume of 2 to 4nm to the total pore volume was 8.7%), the ratio of the pore volume of 100-300nm to the total pore volume was 7.8%, the pore volume was 0.32mL/g, and the average pore diameter was 7.8 nm.
Preparation example 4
The procedure of preparation 3 was followed. In the step (1), a VIII group metal element is not introduced, a VIB group metal element W with the same amount is introduced, a tungsten source is ammonium metatungstate, and the rest is the same, so that the hydrofining catalyst Z-4 is obtained.
Comparative preparation example 1
Commercially available white carbon black (specific surface area: 220 m)2The average pore diameter is 12.7nm), and basic cobalt carbonate powder are uniformly mixed without a roasting step to obtain the inorganic refractory powder containing cobalt. Wherein the amount of basic cobalt carbonate used corresponds to a cobalt (calculated as cobalt oxide) content of the catalyst of 22.0 wt.%. Then, an impregnation solution was prepared in accordance with the procedure (2) of preparation example 1, and a catalyst was prepared in accordance with the procedure (3) of preparation example 1, and the composition of the inorganic refractory component and the metal in the dry basis of the catalyst was the same as that of the catalyst in preparation example 1, to obtain a hydrorefined catalyst D-1.
Comparative preparation example 2
A catalyst was prepared by extruding the inorganic refractory precursor, the active component precursor, and the organic alcohol and organic acid used in preparation example 1, and the content of the inorganic refractory component, the content of the active metal component, and the amounts of the organic alcohol and organic acid in the dry basis of the catalyst were maintained the same as in preparation example 1, to obtain a hydrorefining catalyst D-2.
Comparative preparation example 3
A hydrorefining catalyst D-3 was obtained by following the procedure of preparation example 3 except that the organic alcohol and the organic acid were not added in the preparation of the active component solution, and the same operation was repeated.
Comparative preparation example 4
The procedure of preparation 3 was followed. In the step (1), the VIII group metal element is not introduced, the VIII group metal element is completely introduced in the step (2), and the rest is the same, so that the hydrofining catalyst D-4 is obtained.
Example 1
The slurry gas oil A was used as the feed oil, and the process flow shown in FIG. 1 was followed. Firstly, carrying out contact reaction on slurry bed light oil A and a hydrofining catalyst Z-1 in a hydrofining reaction zone to obtain a hydrofining reaction effluent, then carrying out contact reaction on the hydrofining reaction effluent and a hydrofining catalyst RIC-3 in a hydro-upgrading reaction zone, and cutting the hydro-upgrading reaction effluent into tower top gas, naphtha products and diesel products in a fractionating system.
Wherein the volume ratio of the dosage of the hydrofining catalyst to the dosage of the hydro-upgrading catalyst is 1: 2.
The process conditions and the product properties of the fractions are shown in tables 2 and 3, respectively.
Example 2
The slurry bed light oil B was used as a raw material, and the process flow shown in FIG. 1 was followed. Firstly, carrying out contact reaction on slurry bed light oil B and a hydrofining catalyst Z-1 in a hydrofining reaction zone to obtain a hydrofining reaction effluent, then carrying out contact reaction on the hydrofining reaction effluent and a hydrofining catalyst RIC-3 in a hydro-upgrading reaction zone, and cutting the hydro-upgrading reaction effluent into tower top gas, naphtha products and diesel products in a fractionating system.
Wherein the volume ratio of the dosage of the hydrofining catalyst to the dosage of the hydro-upgrading catalyst is 1: 1. The top of the hydrogenation refining reaction zone is filled with a hydrogenation protective agent RG-30A, and the bottom of the hydrogenation modification reaction zone is filled with a hydrogenation refining catalyst Z-1 as a supplementary refining catalyst; the loading amount of the hydrogenation protection is 10 volume percent based on the total amount of the hydrogenation protective agent and the hydrofining catalyst; the loading of the post-purification catalyst was 10 vol% based on the total amount of the hydro-upgrading catalyst and the post-purification catalyst.
The process conditions and the product properties of the fractions are shown in tables 2 and 3, respectively.
Example 3
The slurry gas oil C was used as the feed oil, and the process flow shown in FIG. 1 was followed. Firstly, carrying out contact reaction on the slurry bed light oil C and a hydrofining catalyst Z-2 in a hydrofining reaction zone to obtain a hydrofining reaction effluent, and then carrying out contact reaction on the hydrofining reaction effluent and a hydrofining catalyst RHC-210 in a hydro-upgrading reaction zone. And cutting the effluent of the hydro-upgrading reaction into tower top gas, naphtha product, aviation kerosene product and diesel oil product in a fractionating system.
Wherein the volume ratio of the dosage of the hydrofining catalyst to the dosage of the hydro-upgrading catalyst is 1: 4. The top of the hydrogenation refining reaction zone is filled with a hydrogenation protective agent RG-30B, and the bottom of the hydrogenation modification reaction zone is filled with a hydrogenation refining catalyst Z-2 serving as a supplementary refining catalyst; the loading amount of the hydrogenation protection is 10 volume percent based on the total amount of the hydrogenation protective agent and the hydrofining catalyst; the loading of the post-purification catalyst was 10 vol% based on the total amount of the hydro-upgrading catalyst and the post-purification catalyst.
The process conditions and the product properties of the fractions are shown in tables 2 and 3, respectively.
Example 4
The slurry gas oil A was used as the feed oil, and the process flow shown in FIG. 2 was followed. Firstly, mixing slurry bed light oil A and circulating diesel oil, then entering a hydrofining reaction zone to perform contact reaction with a hydrofining catalyst Z-2 to obtain a hydrofining reaction effluent, then performing contact reaction on the hydrofining reaction effluent and a hydro-upgrading catalyst RHC-210 in a hydro-upgrading reaction zone, and cutting the hydro-upgrading reaction effluent into tower top gas, naphtha products, aviation kerosene products and diesel oil products in a fractionation system. Partial diesel oil product
Wherein the volume ratio of the dosage of the hydrofining catalyst to the dosage of the hydro-upgrading catalyst is 1: 1. Hydrogenation protective agents RG-30A and RG-30B are filled at the top of the hydrogenation modification reaction zone, and a hydrogenation refining catalyst Z-2 serving as a supplementary refining catalyst is filled at the bottom of the hydrogenation modification reaction zone; the loading amount of the hydrogenation protection is 10 volume percent based on the total amount of the hydrogenation protective agent and the hydrofining catalyst; the loading of the post-purification catalyst was 10 vol% based on the total amount of the hydro-upgrading catalyst and the post-purification catalyst.
The process conditions and the product properties of the fractions are shown in tables 2 and 3.
Example 5
The procedure is as in example 1, except that the hydrofinishing catalyst Z-1 is replaced by hydrofinishing catalyst Z-3 and the product properties of the fractions are shown in Table 3.
Example 6
The procedure is as in example 1, except that the hydrofinishing catalyst Z-1 is replaced by hydrofinishing catalyst Z-4 and the product properties of the fractions are shown in Table 3.
Comparative examples 1 to 4
The procedure was carried out as in example 1, except that the hydrofinishing catalyst Z-1 was replaced with the hydrofinishing catalyst D-1, the hydrofinishing catalyst D-2, the hydrofinishing catalyst D-3 and the hydrofinishing catalyst D-4, respectively, and the properties of the respective fractions are shown in Table 4.
Comparative example 5
And (3) carrying out contact reaction on the slurry-state bed light oil A and a hydrofining catalyst RN-410 in a hydrofining reaction zone, and cutting tower top gas, naphtha products and diesel products from hydrofining reaction effluent in a fractionation system.
The process conditions and the product properties of the fractions are shown in tables 2 and 4.
As can be seen from the results in Table 4, the method provided by the invention can produce naphtha, aviation kerosene and diesel oil products from slurry bed light oil, and the produced naphtha product has the sulfur content and the nitrogen content of less than 0.5 mu g/g and can be used as a high aromatic hydrocarbon potential reforming raw material; the aviation kerosene product can be used as a high-quality No. 3 jet fuel; the diesel oil can be used as clean diesel oil of national VI standard or used as ethylene cracking raw material.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 5 | |
| Raw oil | Starting materials A | Raw material B | Raw material C | Starting materials A | Starting materials A |
| Hydrofining reaction zone | |||||
| Partial pressure of hydrogen/MPa | 10.5 | 8.5 | 12.5 | 14.0 | 10.5 |
| Purification reaction temperature/. degree.C | 355 | 355 | 365 | 350 | 365 |
| Volume space velocity/h-1 | 1.2 | 1.2 | 1.2 | 1.0 | 0.8 |
| Volume ratio of hydrogen to oil in standard state | 1000 | 1000 | 800 | 600 | 600 |
| Hydro-upgrading reaction zone | |||||
| Partial pressure of hydrogen/MPa | 10.3 | 8.3 | 12.3 | 13.8 | |
| Modification reaction temperature/. degree.C | 360 | 365 | 370 | 360 | |
| Volume space velocity/h-1 | 2.4 | 2.4 | 2.0 | 1.7 | |
| Volume ratio of hydrogen to oil in standard state | 1200 | 1200 | 1200 | 1000 |
TABLE 3
TABLE 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Raw oil | Starting materials A | Starting materials A | Starting materials A | Starting materials A | Starting materials A |
| Product distribution/% | |||||
| Naphtha (a) | 28.0 | 27.2 | 24.5 | 26.7 | 22.3 |
| Aviation kerosene | 0 | 0 | 0 | 0 | 0 |
| Clean diesel oil | 72.0 | 71.8 | 75.5 | 73.3 | 77.7 |
| Product Properties | |||||
| Naphtha (<165℃) | |||||
| Density/(g/cm)3) | 0.740 | 0.738 | 0.729 | 0.733 | 0.723 |
| Sulfur content/(μ g/g) | 0.6 | 0.8 | 1.0 | 1.6 | 2.2 |
| Nitrogen content/(μ g/g) | 1.6 | 1.3 | 0.9 | 0.7 | 2.4 |
| Length of ar | 38.9 | 37.5 | 36.8 | 37.2 | 36.1 |
| Diesel oil product | |||||
| Range of distillation range/. degree.C | >165 | >165 | >165 | >165 | >165 |
| Density (20 ℃ C.)/(g/cm)3) | 0.8289 | 0.8321 | 0.8401 | 0.8387 | 0.8456 |
| Sulfur content/(μ g/g) | 5.1 | 6.4 | 7.5 | 7.1 | 8.2 |
| Polycyclic aromatic hydrocarbon content/%) | 2.0 | 2.2 | 3.1 | 2.8 | 3.4 |
| Total aromatic content/%) | 14.9 | 16.3 | 21.3 | 19.8 | 23.7 |
| Paraffin content/%) | 35.8 | 34.2 | 32.2 | 33.1 | 30.1 |
| Cetane number | 51.0 | 49.8 | 48.8 | 49.8 | 47.3 |
| Cetane index | 50.7 | 50.1 | 48.8 | 49.8 | 46.9 |
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (35)
1. A method of treating slurry bed light oil, the method comprising: carrying out a first contact reaction on the slurry bed light oil and hydrogen with a hydrofining catalyst to obtain a hydrofining reaction effluent, then carrying out a second contact reaction on the hydrofining reaction effluent and a hydro-upgrading catalyst to obtain a hydro-upgrading reaction effluent, and fractionating the hydro-upgrading reaction effluent;
the light oil in the slurry bed has a distillation range of 50-400 deg.C and a density of 0.80-0.90g/cm3The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%;
wherein the hydrofining catalyst contains an inorganic refractory component, a hydrodesulfurization catalytic active component, alcohol and carboxylic acid;
the inorganic refractory component contains at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and part of hydrodesulfurization catalytic active component;
the hydrofining catalyst has a pore diameter of 2-40nm and a pore diameter of 100-300nm, wherein the pore volume of the pore diameter of 2-40nm accounts for 60-95% of the total pore volume, and the pore volume of 100-300nm accounts for 0.5-30% of the total pore volume.
2. The process according to claim 1, wherein the hydrodesulphurization catalytically active component comprises elements of group VIII metals and elements of group VIB metals;
wherein, in the hydrofining catalyst, the content of the VIII group metal element is 15-35 wt% based on the dry weight of the catalyst and calculated by oxide; the content of the group VIB metal elements is 35-75 wt%.
3. The process according to claim 2, wherein the group VIII metal element is contained in the hydrofinishing catalyst in an amount of 20 to 30% by weight, calculated as the oxide and based on the dry weight of the catalyst; the content of the VIB group metal element is 40-65 wt%.
4. The method according to claim 2, wherein the group VIII metal element is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, and the group VIB metal element is selected from at least one of chromium, molybdenum and tungsten.
5. The process of claim 2 wherein the portion of the hydrodesulfurization catalytically active component is a portion of the group VIII metal element in an amount of from 60 to 90 wt.% of the total group VIII metal element content.
6. The process as claimed in any one of claims 1 to 5, wherein in the hydrorefining catalyst, the pore volume at a pore diameter of 2 to 40nm accounts for 75 to 90% of the total pore volume, and the pore volume at a pore diameter of 100 and 300nm accounts for 5 to 15% of the total pore volume.
7. The process of any one of claims 1-5, wherein the hydrofinishing catalyst is a shaped catalyst having a shape selected from at least one of cylindrical, clover, tetrafoil, and honeycomb shapes.
8. The process according to any one of claims 1 to 5, wherein the hydrofinishing catalyst has a specific surface area of from 70 to 200m2Per g, pore volume of 0.15-0.6mL/g, average pore diameter of 5-25 nm.
9. The process of any of claims 1-5, wherein in the hydrofinishing catalyst, the pore volume from 2 to 4nm does not exceed 10% of the total pore volume.
10. A process as claimed in any one of claims 1 to 5, wherein the inorganic refractory component is present in the hydrofinishing catalyst in an amount of from 5 to 40% by weight, based on the dry weight of the catalyst.
11. The process according to claim 10, wherein the inorganic refractory component is contained in the hydrofinishing catalyst in an amount of 10 to 30% by weight, based on the dry weight of the catalyst.
12. A process as claimed in any one of claims 1 to 5, wherein the weight ratio, on a dry basis, of carboxylic acid to inorganic refractory component is in the range 0.002 to 0.1: 1.
13. the method of claim 12, wherein the weight ratio of carboxylic acid to inorganic refractory component on a dry basis is from 0.02 to 0.06: 1.
14. the method of any one of claims 1-5, wherein the carboxylic acid is selected from at least one of a C1-18 mono-saturated carboxylic acid, C7-10 phenyl acid, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, and tartaric acid.
15. The method of any of claims 1-5, wherein the ratio of moles of alcohol to dry weight of the inorganic refractory component is from 0.005 to 0.03: 1.
16. the method of claim 15, wherein the ratio of moles of alcohol to dry weight of the inorganic refractory component is from 0.01 to 0.02: 1.
17. the method according to any one of claims 1 to 5, wherein the alcohol is at least one selected from the group consisting of C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, and trimethylolethane.
18. The process of any of claims 1-5, wherein the hydrofinishing catalyst further comprises phosphorus, based on the dry weight of the catalyst and P2O5The content of the phosphorus element is 0.8-10 wt%.
19. The process of claim 18 wherein the hydrofinishing catalyst further comprises phosphorus, based on the dry weight of the catalyst and P2O5The content of the phosphorus element is 1-8 wt%.
20. The process of any one of claims 1-5, wherein the hydrofinishing catalyst is prepared by a process comprising:
(1) mixing and roasting a precursor containing at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and a precursor of a part of hydrodesulfurization catalytic active component to obtain an inorganic refractory component;
(2) mixing alcohol, carboxylic acid and the precursor of the residual hydrodesulfurization catalytic active component to obtain impregnation liquid;
(3) and mixing the inorganic refractory component with the impregnation liquid, and molding and drying the obtained mixture to obtain the hydrofining catalyst.
21. The method of claim 20, wherein the impregnating solution obtained in step (2) further contains a phosphorus-containing substance.
22. The method of claim 21, wherein the phosphorus-containing substance is selected from at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate, and ammonium dihydrogen phosphate.
23. The method of claim 20, wherein in step (1), the roasting conditions comprise: the roasting temperature is 300-900 ℃; the roasting time is 1-15 h.
24. The method of claim 23, wherein in step (1), the roasting conditions comprise: the roasting temperature is 400-800 ℃; the roasting time is 3-8 h.
25. The method of claim 20, wherein in step (3), the drying conditions comprise: the drying temperature is 50-250 ℃; the drying time is 2-10 h.
26. The method of claim 25, wherein in step (3), the drying conditions comprise: the drying temperature is 100-200 ℃; the drying time is 3-8 h.
27. The method of claim 20, wherein the silica precursor is at least one of silica sol, silica white, and silica dioxide; the magnesium oxide precursor is at least one of magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium acetate and magnesium oxide; the precursor of the calcium oxide is at least one of calcium hydroxide, calcium carbonate, calcium oxalate, calcium nitrate, calcium acetate and calcium oxide; the zirconia precursor is at least one of zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium acetate and zirconia; the precursor of the titanium oxide is at least one of titanium hydroxide, titanium nitrate and titanium acetate.
28. The method of claim 20, wherein the silica, magnesia, calcia, zirconia, and titania precursors have an average pore diameter of no less than 10nm, a pore volume fraction of 2-6nm pore diameter of no more than 15% of the total pore volume, and a pore volume fraction of 6-40nm pore diameter of no less than 75% of the total pore volume.
29. The process according to any one of claims 1 to 5, wherein the hydro-upgrading catalyst comprises a support and a metal component supported on the support; the carrier contains amorphous silicon-aluminum and a molecular sieve; the amorphous silicon-aluminum comprises aluminum oxide and silicon oxide-aluminum oxide with a pseudo-boehmite structure; the molecular sieve is selected from at least one of faujasite, mordenite, L-type zeolite, omega zeolite, Y-type zeolite and Beta zeolite; the metal components are VIB group metal elements and VIII group metal elements.
30. The method of claim 29, wherein the metal component is selected from at least one of Mo, W, Co, and Ni.
31. The process of claim 29, wherein the alumina-silica is present in an amount of 1 to 70 wt.%, the molecular sieve is present in an amount of 1 to 60 wt.%, and the alumina is present in an amount of 5 to 80 wt.%, based on the total amount of the hydro-upgrading catalyst; calculated by oxide, the content of VIII group metal elements is 1-15 wt%, and the content of VIB group metal elements is 10-40 wt%.
32. The method of any one of claims 1-5, wherein the conditions under which the first contact reaction is carried out comprise: the hydrogen partial pressure is 8.0-14.0 MPa; the temperature is 300-450 ℃; the volume ratio of hydrogen to oil is 500-1500; the liquid hourly space velocity is 0.5-4.0h-1。
33. The method of claim 32, wherein the conditions under which the first contact reaction is carried out comprise: the hydrogen partial pressure is 8.5-14.0 MPa;the temperature is 350-430 ℃; the volume ratio of hydrogen to oil is 600-1200; the liquid hourly space velocity is 0.5-2.0h-1。
34. The method of any one of claims 1-5, wherein the conditions under which the second contact reaction is carried out comprise: the hydrogen partial pressure is 8.0-14.0 MPa; the temperature is 300-450 ℃; the volume ratio of hydrogen to oil is 500-1500; the liquid hourly space velocity is 0.5-4.0h-1。
35. The method of claim 34, wherein the conditions under which the second contact reaction is carried out comprise: the hydrogen partial pressure is 8.3-13.8 MPa; the temperature is 370 ℃ and 430 ℃; the volume ratio of hydrogen to oil is 600-1200; the liquid hourly space velocity is 0.5-2.5h-1。
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| CN103769220A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for distillate oil hydro-treatment |
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| CN103059977A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing high-quality low-freezing diesel oil |
| CN103769220A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for distillate oil hydro-treatment |
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