CN114686256A - Grading method of hydrocracking catalyst - Google Patents
Grading method of hydrocracking catalyst Download PDFInfo
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- CN114686256A CN114686256A CN202011620203.2A CN202011620203A CN114686256A CN 114686256 A CN114686256 A CN 114686256A CN 202011620203 A CN202011620203 A CN 202011620203A CN 114686256 A CN114686256 A CN 114686256A
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- hydrocracking
- reaction zone
- catalyst
- mass fraction
- reaction
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002283 diesel fuel Substances 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003223 protective agent Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 25
- 238000005336 cracking Methods 0.000 description 21
- 239000002994 raw material Substances 0.000 description 18
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 14
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 11
- 108091006230 SLC7A3 Proteins 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 9
- 108091006231 SLC7A2 Proteins 0.000 description 9
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 8
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 8
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 7
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 7
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 7
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000002860 competitive effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a grading method of a hydrocracking catalyst. Raw oil and hydrogen enter a hydrofining reaction zone together, and the hydrofining reaction effluent directly enters a hydrocracking reactor without separation and sequentially contacts and reacts with more than two hydrocracking catalyst beds; wherein, compared with the adjacent upstream catalyst bed layer, the mass fraction of NiO is reduced, the mass fraction of CoO is increased, and MoO is increased in the downstream catalyst bed layer along the material flow direction3The mass fraction is reduced, the mass fraction of the total active metal oxides is reduced, and the molecular sieve content is reduced. The method reduces the hydrocracking reaction temperature by reasonably grading different bed hydrocracking catalysts under the condition of the same conversion rate.
Description
Technical Field
The invention relates to a grading method of a hydrocracking catalyst, in particular to a grading method of a one-stage (series) hydrocracking process catalyst.
Background
The hydrocracking technology has the characteristics of high production flexibility, strong raw material adaptability and high product quality, and plays a role of a medium-flow column in the aspect of adjusting the production balance of a whole plant. The products of the hydrocracking process include natural gas, liquefied gas, naphtha, jet fuel, diesel, and tail oil. The hydrocracking tail oil is rich in naphthenes and paraffins, and can be used as a high-quality ethylene raw material or lubricating oil base oil prepared by steam cracking. However, for oil refining enterprises without subsequent ethylene production devices or isomerization dewaxing devices, the tail oil fraction can only be sold at low price, and the economic benefit is not good. Therefore, how to efficiently convert the hydrocracking tail oil fraction into high value-added fractions such as naphtha, jet fuel, diesel oil and the like has important significance for improving the economic benefit of oil refining enterprises.
In hydrocracking technology, there are many reports on the grading of hydrocracking catalysts. CN1088094C discloses a grading method of hydrocracking catalyst, which uses traditional molecular sieve type and/or amorphous silicon-aluminum hydrocracking catalyst, when filling hydrocracking catalyst, selects hydrocracking catalyst with different activity and/or different nitrogen resistance, but basically equivalent selectivity of target product, can reduce 30% -70% cold hydrogen consumption or improve 20% -50% hydrocracking unit treatment capacity, and brings great economic benefit for enterprise.
CN1508232A discloses a full-cycle hydrocracking process, which adopts a process route of cracking first and then refining, tail oil is circulated back to a cracking section for hydrocracking reaction, and hydrocracking catalysts with different performances are graded and filled in a cracking reactor. Compared with the prior art, the process has the advantages of high overall activity, good product quality, low operation cost and the like, and is mainly used for producing high-quality clean fuel.
CN106669861A discloses a hydrocracking catalyst grading method and a catalytic diesel oil hydro-conversion process. The hydrocracking catalyst grading method equally divides a hydrocracking reactor into a plurality of reaction zones along the material flowing direction, a hydrocracking catalyst and a regenerated catalyst are mixed and filled in each reaction zone, and the mass ratio of the hydrocracking catalyst to the regenerated catalyst in each reaction zone is gradually reduced along the material flowing direction. The invention improves the hydrogenation selectivity of diesel oil/gasoline components in the conversion process and improves the yield of high-octane gasoline products by filling catalysts with different reaction performances in a grading manner in the cracking reactor.
CN105018137A discloses a hydrocracking method for producing high-quality jet fuel with low energy consumption. Raw oil and hydrogen are mixed and then pass through a hydrofining zone and a first cracking reaction zone, and middle distillate oil obtained by separation enters a second cracking reaction zone to be cracked; wherein the first cracking reaction zone at least comprises two cracking catalysts, and the content of the Y molecular sieve of the two catalysts is gradually reduced. The invention organically combines the high-temperature high-pressure countercurrent heat transfer technology with the hydrocracking catalyst grading technology, comprehensively utilizes the hydrocracking reaction heat, maintains the selectivity of the catalyst, improves the quality of target products, and reduces the engineering investment and the operation energy consumption.
Disclosure of Invention
The invention aims to provide a grading method of a hydrocracking catalyst. The hydrocracking reaction temperature is reduced under the condition of the same conversion rate by reasonably grading the molecular sieve content and the active metal composition in the hydrocracking catalysts in different reaction zones.
After research, the inventor of the application finds that compared with a NiMoS active phase, a CoMoS active phase wafer is small, the adsorption performance of reactants is strong, the activation energy required for dissociating hydrogen to generate activated hydrogen is low, the carbon deposition rate is slow, and the high-temperature stability is good. When the mixture of polycyclic aromatic hydrocarbon and alkane is used as raw material, the CoMo type hydrocracking catalyst has strong alkane cracking capability and is slightly influenced by competitive adsorption of polycyclic aromatic hydrocarbon. The NiMo type hydrocracking catalyst has strong monocyclic aromatic hydrocarbon conversion capacity, can deeply saturate polycyclic aromatic hydrocarbon and convert the polycyclic aromatic hydrocarbon into naphthenic hydrocarbon, but has poor high-temperature stability, paraffin adsorption and weak cracking capacity. Based on the Mo type hydrocracking catalyst, the auxiliary agent cobalt can increase the competitive adsorption capacity of the active phase reactants, and the auxiliary agent nickel can reduce the competitive adsorption capacity of the reactants. In the traditional hydrocracking reactor, the content of alkane and naphthene is gradually increased and the hydrogen partial pressure is gradually reduced along the material flow direction. Therefore, if the metal composition of the hydrocracking catalyst in each reaction zone is flexibly adjusted according to the reaction characteristics of different reaction zones of hydrocracking, the reactants can be maximally converted to generate high value-added components such as naphtha, jet fuel and diesel oil.
Aiming at the defects in the prior art, the invention provides a grading method of a hydrocracking catalyst.
The grading method of the hydrocracking catalyst comprises the following steps:
(1) providing a hydrofining reaction zone, wherein the hydrofining reactor comprises a hydrofining catalyst; providing a hydrocracking reaction zone, wherein the hydrocracking reactor is filled with a hydrocracking catalyst and an optional post-refining agent;
(2) raw oil and hydrogen enter a hydrofining reaction zone together, and contact-react with a hydrofining catalyst; the effluent of the hydrorefining reaction directly enters a hydrocracking reactor without separation, and sequentially contacts and reacts with more than two hydrocracking catalyst beds;
(3) and carrying out gas-liquid separation and fractionation on the reaction effluent obtained by hydrocracking to obtain a gas product and a liquid product containing components of naphtha, jet fuel, diesel oil and tail oil.
In the invention, the raw material is wax oil raw material, the initial boiling point of the wax oil raw material is generally 250-350 ℃, and the final boiling point of the wax oil raw material is generally 500-580 ℃. When processing inferior raw materials with high metal content, silicon content and carbon residue, a protective agent is generally filled before a hydrofining agent, and the protective agent comprises a demetallizing agent, a carbon residue removing agent, a silicon capturing agent and the like.
In the step (1), the hydrofining reaction zone is generally divided into 1-6 hydrofining catalyst beds along the material flow direction, and preferably divided into 2-4 catalyst beds; the hydrocracking reaction zone is generally divided into 2-6 hydrocracking catalyst beds along the material flow direction, and preferably 3-5 hydrocracking catalyst beds.
In the process of the present invention, the hydrofinishing catalyst is generally composed of a support and a metal. The metal is non-noble metal, the main active metal is the VIB metal component in the periodic table of elements, such as tungsten or/and molybdenum, and the weight of the metal oxide is 5-50 wt%, preferably 10-40 wt%. The auxiliary agent is mainly a metal component in the VIII B in the periodic table of elements, such as cobalt or/and nickel, and the weight of the auxiliary agent is 2-30 wt%, preferably 3-15 wt% based on the weight of metal oxide. The carrier can be a single carrier or a mixture of alumina, amorphous silicon aluminum and a molecular sieve, and the carrier is 45-90 wt%, preferably 50-85 wt%. The above carrier may be used to carry an active metal and prepare a hydrorefining catalyst, or an industrial catalyst such as FF-46, FF-56, and FF-66 from the Coulter petrochemical research institute may be used.
In the process of the present invention, the hydrocracking catalyst generally comprises a cracking component, a hydrogenation component and a binder. The cracking component typically comprises amorphous silica-alumina and/or molecular sieves, typically molecular sieves such as Y-type or beta-type molecular sieves. The binder is typically alumina or silica. The hydrogenation component is a metal, a metal oxide or a metal sulfide of a metal in a VI group, a VII group or a VIII group, and more preferably one or more of iron, chromium, molybdenum, tungsten, cobalt, nickel or sulfides or oxides thereof. The metal component is generally present in an amount of 10 to 35 wt.% as oxide, based on the weight of the catalyst.
In the hydrocracking reaction zone, compared with an adjacent upstream catalyst bed layer, the mass fraction of NiO of a downstream catalyst bed layer is reduced by 0.5-5.0 percent along the material flow direction; the mass fraction of CoO is increased, preferably by 0.5-5.0 percent; MoO3The mass fraction is reduced, preferably by 1.5-5.0 percentage points; the total metal mass fraction is reduced, preferably by 1.5-8.0 percentage points; the mass content of the molecular sieve is reduced, and is preferably 4.0-10.0 percent lower.
In one or more embodiments of the process of the present invention, the hydrocracking catalyst in step (2) is prepared as follows: taking a Y molecular sieve as an acidic material and alumina as an adhesive, kneading, molding, drying and roasting the materials to prepare a carrier; respectively dipping molybdenum, nickel and cobalt active metals by using nickel nitrate as a nickel source, cobalt nitrate hexahydrate as a cobalt source and ammonium molybdate tetrahydrate as a molybdenum source by adopting a two-step isometric dipping method, roasting at 400-550 ℃, and preparing NiCoMo/Y-Al2O3Catalyst based on the mass of the catalystThe mass fraction of nickel oxide is 1.0-8.0%, the mass fraction of CoO is 1.0-8.0%, the mass fraction of molybdenum oxide is 10.0-20.0%, and the mass fraction of Y molecular sieve in the carrier is 20.0-45.0%.
In the step (2), the reaction conditions in the hydrofining and hydrocracking reactor are generally as follows: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, and preferably 270-450 ℃; the volume space velocity is 0.1-15.0 h-1Preferably 0.2 to 3.0 hours-1(ii) a The volume ratio of the hydrogen to the oil is 100: 1-2500: 1, preferably 400: 1-2000: 1.
In step (3), the resulting liquid product is hydrocracked, typically also including at least one of light naphtha, heavy naphtha, aviation kerosene, diesel and tail oil fractions. Furthermore, the obtained tail oil or/and diesel oil can be taken as a product out of the device, and can also be recycled to the inlet of a hydrofining reactor or a hydrocracking reactor, so that the yield of the target product is increased.
In the present invention, the hydrofining reaction zone may include one or more reactors, the hydrocracking reaction zone may also include one or more reactors, or the hydrofining reaction zone and the hydrocracking reaction zone may be disposed in one reactor.
The hydrocracking catalyst grading method can be used in any hydrocracking field.
Compared with the prior art, the method has the following beneficial effects:
1. according to the research of the inventor, the hydrocracking catalyst is graded along the direction of the hydrocracking reactor material according to the reaction characteristics of different reaction zones in the hydrocracking reactor. The upper part of the reactor has high aromatic hydrocarbon content and low reaction temperature, and is filled with a hydrocracking catalyst with high NiO content preferentially, so that the hydrocracking catalyst can adsorb aromatic hydrocarbon preferentially and perform ring-opening cracking reaction at a lower temperature. The lower part of the reactor is filled with hydrocracking catalyst with high content of naphthene and paraffin and high content of CoO, which can increase the adsorption selectivity of paraffin and naphthene, carry out deep cracking chain-breaking reaction and convert into light fraction. The middle part of the reactor is filled with a hydrocracking catalyst with moderate metal composition and content, so that the transition of reaction activity and selectivity is realized.
2. The invention carries out grading on the content of the molecular sieve, along the material flow direction, the cracking activity of the catalyst is gradually reduced, the stable transition of the reaction temperature can be realized, and the cold hydrogen quantity and the energy consumption of the device are reduced.
3. The reaction temperature of the hydrocracking reactor is gradually increased along the material flow direction, and the hydrogen partial pressure is gradually reduced. The addition of the auxiliary agent Co can increase the high-temperature stability of the catalyst, and the hydrocracking catalyst adopts a grading mode that the CoO content is gradually increased, so that the lower bed layer catalyst can exert hydrocracking activity in the atmosphere with high hydrogen partial pressure and reaction temperature.
4. In the hydrocracking reactor, along the material flow direction, the content of aromatic hydrocarbon is gradually reduced, and the content of naphthenic hydrocarbon and paraffin hydrocarbon is gradually increased. The total loading capacity of the active metal is gradually reduced, the composition characteristics of various reactants in different reaction zones can be matched, the cost of the catalyst can be reduced, and the quality of target products can be improved.
Detailed Description
The process of the present invention will be further illustrated with reference to the following examples, but the invention is not limited thereto.
TABLE 1 Properties of the stock oils
TABLE 2 commercial catalysts
TABLE 3 catalyst essential Properties
TABLE 4 reaction conditions
CAT-1, CAT-2, CAT-3, CAT-4 and CAT-5 catalysts in Table 3 use the same alumina and Y molecular sieves, and the preparation method is as follows:
CAT-1: alumina and a Y molecular sieve are used as carriers, wherein the mass fractions of the Y molecular sieve and the alumina are respectively 44% and 27.5%. Alumina is used as a binder, and the carrier is kneaded, molded and dried. Respectively taking cobalt nitrate hexahydrate as a cobalt source, nickel nitrate as a nickel source and ammonium molybdate tetrahydrate as a molybdenum source, and respectively impregnating molybdenum, cobalt and nickel active metals by adopting a two-step isometric impregnation method. Roasting twice at 550 ℃ to prepare NiCoMo/Y-Al2O3The catalyst comprises, by mass, 19.5% of molybdenum oxide, 7.0% of nickel oxide and 2.0% of cobalt oxide.
And (3) CAT-2: alumina and a Y molecular sieve are used as carriers, wherein the mass fractions of the Y molecular sieve and the alumina are respectively 35.5% and 38.0%. Alumina is used as a binder, and the carrier is kneaded, molded and dried. Respectively taking cobalt nitrate hexahydrate as a cobalt source, nickel nitrate as a nickel source and ammonium molybdate tetrahydrate as a molybdenum source, and respectively impregnating molybdenum, cobalt and nickel active metals by adopting a two-step isometric impregnation method. Roasting twice at 550 ℃ to prepare NiCoMo/Y-Al2O3The catalyst comprises, based on the mass of the catalyst, 17.5% of molybdenum oxide, 6.0% of nickel oxide and 3.0% of cobalt oxide.
And (3) CAT-3: alumina and a Y molecular sieve are used as carriers, wherein the mass fractions of the Y molecular sieve and the alumina are 32.0% and 43.5%, respectively. Alumina is used as a binder, and the carrier is kneaded, molded and dried. Respectively taking cobalt nitrate hexahydrate as a cobalt source, nickel nitrate as a nickel source and ammonium molybdate tetrahydrate as a molybdenum source, and respectively impregnating molybdenum, cobalt and nickel active metals by adopting a two-step isometric impregnation method. Roasting twice at 550 ℃ to prepare NiCoMo/Y-Al2O3The catalyst comprises 15.5% of molybdenum oxide, 5.0% of nickel oxide and 4.0% of cobalt oxide by mass based on the mass of the catalyst.
And (5) CAT-4: using alumina and Y molecular sieve as carriers, whereinThe mass fractions of the Y molecular sieve and the alumina are respectively 26.0% and 51.5%. Alumina is used as a binder, and the carrier is kneaded, molded and dried. Respectively taking cobalt nitrate hexahydrate as a cobalt source, nickel nitrate as a nickel source and ammonium molybdate tetrahydrate as a molybdenum source, and respectively impregnating molybdenum, cobalt and nickel active metals by adopting a two-step isometric impregnation method. Roasting twice at 550 ℃ to prepare NiCoMo/Y-Al2O3The catalyst comprises 13.5% of molybdenum oxide, 3.5% of nickel oxide and 5.5% of cobalt oxide by mass based on the mass of the catalyst.
CAT-5: alumina and a Y molecular sieve are used as carriers, wherein the mass fractions of the Y molecular sieve and the alumina are respectively 20.0% and 60.0%. Alumina is used as a binder, and the carrier is kneaded, molded and dried. Respectively taking cobalt nitrate hexahydrate as a cobalt source, nickel nitrate as a nickel source and ammonium molybdate tetrahydrate as a molybdenum source, and respectively impregnating molybdenum, cobalt and nickel active metals by adopting a two-step isometric impregnation method. Roasting twice at 550 ℃ to prepare NiCoMo/Y-Al2O3The catalyst comprises 11.0% of molybdenum oxide, 1.0% of nickel oxide and 8.0% of cobalt oxide by mass based on the mass of the catalyst.
The raw oil used in the following examples and comparative examples was Iranian VGO, and the properties thereof are shown in Table 1. The hydrocracking reactor is exemplified by a typical three equally high beds of cracking catalyst. The hydrofinishing agent FF-46 used in the examples and comparative examples was a commercial agent, and the properties of both were as shown in Table 2. The main properties of the prepared CAT-1, CAT-2, CAT-3, CAT-4 and CAT-5 are shown in Table 3. The process evaluation conditions for all examples and comparative examples are shown in Table 4. In the examples and the comparative examples, the distillation range of light naphtha is less than 65 ℃, the distillation range of heavy naphtha is 65-175 ℃, the distillation range of jet fuel is 175-260 ℃, the distillation range of diesel oil is 260-350 ℃, and the distillation range of tail oil is more than 350 ℃.
Example 1
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-1, CAT-2 and CAT-3 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. And using Iran VGO as a raw material, and adopting the process evaluation conditions in the table 4 to cut the cracked product oil by the real boiling point to obtain a hydrocracking product.
Example 2
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-2, CAT-3 and CAT-4 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. And using Iran VGO as a raw material, and adopting the process evaluation conditions in the table 4 to cut the cracked product oil by the real boiling point to obtain a hydrocracking product.
Example 3
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-3, CAT-4 and CAT-5 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. And using Iran VGO as a raw material, and adopting the process evaluation conditions in the table 4 to cut the cracked product oil by the real boiling point to obtain a hydrocracking product.
Example 4
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-1, CAT-2 and CAT-3 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. The Daqing VGO is used as a raw material, and the hydrocracking product is obtained after real boiling point cutting of the cracking product oil by adopting the process evaluation conditions in the table 4.
Example 5
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-2, CAT-3 and CAT-4 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. The Daqing VGO is used as a raw material, and the hydrocracking product is obtained after real boiling point cutting of the cracking product oil by adopting the process evaluation conditions in the table 4.
Example 6
FF-46 refined catalyst is filled in all the hydrofining reactor, and CAT-3, CAT-4 and CAT-5 are filled in three bed layers of the hydrocracking reactor in equal volumes respectively. The Daqing VGO is used as a raw material, and the hydrocracking product is obtained after real boiling point cutting of the cracking product oil by adopting the process evaluation conditions in the table 4.
Comparative example 1
FF-46 refined catalysts are filled in all the hydrofining reactors, and CAT-3 hydrocracking catalysts are filled in all three bed layers of the hydrocracking reactor in equal volumes. And using Iran VGO as a raw material, and adopting the process evaluation conditions in the table 4 to cut the cracked product oil by the real boiling point to obtain a hydrocracking product.
Comparative example 2
FF-46 refined catalysts are filled in all the hydrofining reactors, and CAT-2 hydrocracking catalysts are filled in all three beds of the hydrocracking reactor in equal volumes. The Daqing VGO is used as a raw material, and the hydrocracking product is obtained after real boiling point cutting of the cracking product oil by adopting the process evaluation conditions in the table 4.
Comparative example 3
FF-46 refined catalysts are filled in all the hydrofining reactors, and CAT-1 hydrocracking catalysts are filled in all three beds of the hydrocracking reactor in equal volumes. The Daqing VGO is used as a raw material, and the hydrocracking product is obtained after real boiling point cutting of the cracking product oil by adopting the process evaluation conditions in the table 4.
Comparative example 4
FF-46 refined catalysts are filled in all the hydrofining reactors, and CAT-4 hydrocracking catalysts are filled in all three beds of the hydrocracking reactor in equal volumes. And using Iran VGO as a raw material, and adopting the process evaluation conditions in the table 4 to cut the cracked product oil by the real boiling point to obtain a hydrocracking product.
Table 5 example test results
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Yield of tail oil, wt.% | 24.0 | 24.5 | 23.6 | 24.1 | 25.1 | 25.2 |
| Hydrocracking reaction temperature,. degree.C | 365 | 367 | 366 | 368 | 369 | 370 |
Table 6 comparative example test results
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Yield of tail oil, wt% | 25.5 | 25.8 | 26.6 | 27.1 |
| Hydrocracking reaction temperature of DEG C | 373 | 374 | 375 | 378 |
The experimental results of the comparative example and the example show that the hydrocracking catalyst grading method can effectively improve the conversion rate of more than 350 ℃, and the yield of light naphtha, heavy naphtha, jet fuel and diesel oil products can be obviously increased. When the nitrogen content of the refined oil is less than 10 ppm, the hydrofining reactor is filled with FF-46 hydrofining catalyst, and three beds of the hydrocracking reactor are filled with CAT-1, CAT-2 and CAT-3 in equal volume, the yield of the tail oil is lowest, and the hydrocracking reaction temperature is lowest.
Claims (11)
1. A hydrocracking catalyst grading process comprising the steps of:
(1) providing a hydrofining reaction zone, wherein the hydrofining reactor comprises a hydrofining catalyst; providing a hydrocracking reaction zone, wherein the hydrocracking reactor is filled with a hydrocracking catalyst and an optional post-refining agent;
(2) raw oil and hydrogen enter a hydrofining reaction zone together and are in contact reaction with a hydrofining catalyst; the effluent of the hydrorefining reaction directly enters a hydrocracking reaction zone without separation, and sequentially contacts and reacts with more than two hydrocracking catalyst beds;
(3) carrying out gas-liquid separation and fractionation on reaction effluent obtained by hydrocracking to obtain a gas product and a liquid product containing naphtha, jet fuel, diesel oil and tail oil components;
wherein, in the hydrocracking reaction zone,compared with the adjacent upstream catalyst bed layer, the mass fraction of NiO of the downstream catalyst bed layer is reduced, the mass fraction of CoO is increased, and MoO3The mass fraction is reduced, the mass fraction of the total active metal oxides is reduced, and the mass content of the molecular sieve is reduced.
2. The process of claim 1, wherein the feedstock is a wax oil feedstock having an initial boiling point of 250 to 350 ℃ and an end point of 500 to 580 ℃.
3. The method of claim 1, wherein when processing poor quality feedstock with high metal content, silicon content and carbon residue, the hydrofinishing agent is preceded by a protective agent, and the protective agent comprises at least one of a demetallizing agent, a carbon residue removing agent and a silicon capturing agent.
4. The process of claim 1, wherein the hydrocracking reaction zone comprises 2 to 6 hydrocracking catalyst beds in the stream direction.
5. The process of claim 1 wherein the hydrocracking catalyst comprises an active metal selected from the group consisting of Ni, Co and Mo and a support containing a Y-type molecular sieve.
6. The process of claim 1, wherein the mass fraction of NiO is 0.5 to 5.0 percent lower for a downstream catalyst bed than for an adjacent upstream catalyst bed, and the mass fraction of CoO is 0.5 to 5.0 percent higher for a downstream catalyst bed, and MoO is present in the stream3The mass fraction is 1.5-5.0 percent lower, the total mass fraction of the metal oxide is 1.5-8.0 percent lower, and the content of the molecular sieve is 4.0-10.0 percent lower.
7. The method according to claim 1 or 6, wherein the hydrocracking catalyst comprises, by mass, 1.0-8.0% of nickel oxide, 1.0-8.0% of CoO, 10.0-20.0% of molybdenum oxide and 20.0-45.0% of a molecular sieve.
8. The process of claim 1, wherein the reaction conditions in the hydrofinishing reaction zone and the hydrocracking reaction zone are: the reaction pressure is 5.0-35.0 MPa, the average reaction temperature is 200-480 ℃, and the volume space velocity is 0.1-15.0 h-1The volume ratio of the hydrogen to the oil is 100: 1-2500: 1.
9. The process of claim 8, wherein the reaction conditions in the hydrofinishing reaction zone and the hydrocracking reaction zone are: the reaction pressure is 6.0-19.0 MPa, the average reaction temperature is 270-450 ℃, and the volume space velocity is 0.2-3.0 h-1The volume ratio of hydrogen to oil is 400: 1-2000: 1.
10. The process of claim 1, wherein the tail oil or/and diesel oil obtained in step (3) is discharged from the unit as a product or recycled to the inlet of the hydrofinishing reaction zone or the hydrocracking reaction zone.
11. The process of claim 1 wherein the hydrofinishing reaction zone comprises one or more reactors and the hydrocracking reaction zone comprises one or more reactors, or the hydrofinishing reaction zone and the hydrocracking reaction zone are disposed in a single reactor.
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| CN105001909A (en) * | 2014-04-23 | 2015-10-28 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for low energy consumption production of high-quality jet fuels |
| CN108624357A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil conversion process |
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