CN116023988B - Hydrotreatment method of raw oil with high aromatic hydrocarbon content - Google Patents
Hydrotreatment method of raw oil with high aromatic hydrocarbon content Download PDFInfo
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- CN116023988B CN116023988B CN202111243452.9A CN202111243452A CN116023988B CN 116023988 B CN116023988 B CN 116023988B CN 202111243452 A CN202111243452 A CN 202111243452A CN 116023988 B CN116023988 B CN 116023988B
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- catalyst
- denitrification reaction
- catalyst filled
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000005336 cracking Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
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- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 150000002815 nickel Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 239000012535 impurity Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 20
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 239000011574 phosphorus Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
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- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
Classifications
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hydrotreating method, which comprises the following steps: the raw oil enters a hydrogenation reaction zone and is divided into three sections of reaction zones along the flow direction of a material flow, namely a shallow denitrification reaction zone, an isomerism-shallow pyrolysis reaction zone and a deep denitrification reaction zone, wherein the concentration of nickel atoms on the surface of a hydrotreating catalyst filled in the deep denitrification reaction zone is higher than that (molar concentration) of nickel atoms on the surface of a hydrotreating catalyst filled in the shallow denitrification reaction zone, preferably 3-80% and more preferably 5-30% higher, and the infrared total acid of the catalyst filled in the isomerism-shallow pyrolysis reaction zone is higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone and the deep denitrification reaction zone, preferably 0.05-0.20 mmol/g higher. The method can not only improve the deep denitrification performance of the hydrotreating reactor, but also improve the aromatic saturation performance of the catalyst system.
Description
Technical Field
The invention relates to a hydrotreating method of high-aromatic-content raw oil, in particular to a deep denitrification hydrotreating method of high-aromatic-content raw oil.
Background
In recent years, around the topics of energy conservation, environmental protection, low carbon emission, economic benefit improvement, sustainable development realization and the like, the global improvement is achieved in key technical fields such as coal-to-liquid technology, heavy oil (residual oil) deep processing, clean fuel production, oiling combination, production of alternative fuels and lubricating oil base oil and the like. Hydrocracking technology plays an important role therein.
In modern oil refining technology, hydrocracking refers to the hydrogenation process that more than 10% of macromolecular compounds in raw materials are changed into micromolecular compounds through hydrogenation reaction, and has the characteristics of strong raw material adaptability, large flexibility of production scheme, good product quality and the like, so that the hydrocracking becomes one of important process technologies for deep processing of heavy oil. The heart of the hydrocracking technology is a catalyst, including a pretreatment catalyst and a cracking catalyst. Wherein the hydrocracking pretreatment catalyst has the main functions of: the hydrogenation removes sulfur, nitrogen, oxygen, heavy metal and other impurities contained in the raw materials, and the hydrogenation saturates the polycyclic aromatic hydrocarbon, thereby improving the property of the oil product. Because nitrides, especially basic nitrides, in the feed oil can poison the acid centers of cracking catalysts, hydrodenitrogenation performance is an important indicator for measuring hydrocracking pretreatment catalysts.
CN 112725014A discloses a grading method of a hydrotreating catalyst, the method is to load N catalyst beds, N is an integer greater than 2, wherein the catalyst loaded in the mth catalyst bed has the highest acid content of 250-500 ℃, m is an integer greater than 1 and less than N, the acid content of the catalyst loaded in the catalyst beds from 1 to m is in an increasing trend, the acid content of the catalyst loaded in the catalyst beds from m to N is in a decreasing trend, and the reaction temperature of the catalyst beds is in an increasing trend along the stream. The method can not only improve the total denitrification and desulfurization performance of the hydrotreating reactor, but also improve the stability of the performance of the catalyst system.
CN103805251a discloses a method for producing hydrogenated low-freezing diesel oil by grading technology. After the diesel raw material is mixed with hydrogen, the mixture sequentially passes through at least two hydrogenation reaction areas connected in series, and the hydrogenation reaction areas sequentially comprise a refined modification catalyst composite bed layer and a hydrodewaxing catalyst bed layer which are filled by mixing a hydrofining catalyst and a hydro-modification catalyst according to the material flow direction; and separating and fractionating the reaction effluent obtained in the last hydrogenation reaction zone to obtain the low-condensation-point diesel oil product. The method reasonably combines and utilizes the temperature drop in the hydrodewaxing process and the temperature rise in the hydro-upgrading process, improves the yield of the diesel oil while producing the low-freezing low-sulfur diesel oil, reduces the hot spot temperature of the device and prolongs the operation period; in addition, the consumption of cold hydrogen or the fuel gas consumption of the heating furnace is reduced, and the operation cost is saved.
CN105623717a discloses a hydrogenation catalyst grading method, which comprises: sequentially filling a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrodesulphurisation catalyst, a hydrodenitrogenation catalyst and/or a hydrodecarbonization catalyst along the material flow direction, wherein each of the hydrodemetallization catalyst, the hydrodesulphurisation catalyst, the hydrodenitrogenation catalyst and the hydrodecarbonization catalyst contains at least part of bimodal pore catalysts; in the respective bimodal pore catalysts along the flow direction, the most probable pore diameters of the small pore peaks and the large pore peaks are respectively gradually reduced, the pore volume of the small pore peaks is gradually increased in the share of the total pore volume, and the pore volume of the large pore peaks is gradually reduced in the share of the total pore volume. The invention also discloses a method for carrying out heavy oil hydrotreatment by adopting the hydrogenation catalyst grading method. The method disclosed by the invention can improve the impurity removal rate and prolong the operation period of the heavy oil hydrogenation device.
These methods do not relate to how to improve the deep denitrification performance of the whole reactor. Especially for slurry bed and boiling bed wax oil, the aromatic hydrocarbon content is high, and the aromatic hydrocarbon has more side chain structures, so that the steric hindrance of nitrogen-containing molecules is large, and the denitrification reaction is more difficult to carry out.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hydrotreating method which is suitable for hydrotreating processes of various distillate oil, in particular for processing slurry bed and boiling bed wax oil. The method can not only improve the deep denitrification performance of the hydrotreating reactor, but also improve the aromatic saturation performance of the catalyst system.
A hydrotreating process comprising: the raw oil enters a hydrogenation reaction zone and is divided into three sections of reaction zones along the flow direction of a material flow, namely a shallow denitrification reaction zone, an isomerism-shallow pyrolysis reaction zone and a deep denitrification reaction zone, wherein the concentration of nickel atoms on the surface of a hydrotreating catalyst filled in the deep denitrification reaction zone is higher than that (molar concentration) of nickel atoms on the surface of a hydrotreating catalyst in the shallow denitrification reaction zone, preferably 3-80% and more preferably 5-30% higher, and the infrared total acid of the catalyst filled in the isomerism-shallow pyrolysis reaction zone is higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone and the deep denitrification reaction zone, generally 0.05-0.20 mmol/g and preferably 0.1-0.15 mmol/g higher.
In the method, the volume ratio of the catalyst filled in the three-stage reaction zone is the shallow denitrification reaction zone: isomerism-shallow cleavage reaction zone: deep denitrification reaction zone = 1.0-10.0: 0.2-2.0: 0.5 to 8.0.
In the above method, any one of the reaction zones may be filled with one catalyst or may be filled with a plurality of catalysts in a graded manner, preferably one catalyst. The filling volume ratio of adjacent catalyst beds for filling various catalysts is 1:20-20:1, preferably 1:10-10:1, and more preferably 1:5-5:1.
In the method, the raw materials are various distillate oils, including various diesel oils, VGO, CGO, DAO and mixed oils of two or more of the diesel oils and VGO, CGO, DAO, and the main properties are as follows: the range of the distillation range, the initial distillation point is more than 180 ℃, and the final distillation point is less than 600 ℃; the density is 0.8000-0.9500/g.cm -3 (20 ℃); nitrogen content of 100-8000 mug.g -1; sulfur content is 0.05wt% to 5.0wt% and aromatic hydrocarbon content is 20wt% to 80wt%.
In the method, the raw material passes through a first section of hydrotreating reaction zone to reduce the nitrogen impurity content to less than 300ppm, then passes through the shallow cracking action of a high-acidity catalyst to expose nitrogen-containing hetero atoms, and then enters a deep denitrification reaction zone to achieve the aim of deep denitrification through the denitrification reaction of the hydrotreating catalyst.
In the method, the reaction temperature of the hydrogenation reaction zone is gradually increased, and the reaction temperature is changed according to the reaction raw materials and the reaction conditions. The reaction temperature of the shallow denitrification reaction zone is 280-380 ℃, the reaction temperature of the isomerism-shallow cracking reaction zone is 350-400 ℃, the reaction temperature of the deep denitrification reaction zone is 370-420 ℃, and the average reaction temperature of different reaction zones is sequentially increased by 10-30 ℃ in the same reaction system.
In the method, the shallow denitrification reaction zone is filled with a hydrotreating catalyst; the isomerism-shallow cracking reaction zone is filled with a high-acidity hydrogenation catalyst, and the catalyst contains a strong-acidity component; the deep denitrification reaction zone is filled with a hydrotreating catalyst.
In the above process, the hydrotreating catalyst contains group VIB and group VIII metal components. Wherein the active metal of VIB group is W and/or Mo, the active metal of VIII group is Ni and/or Co, and the active metal in the final hydrotreating catalyst is generally as follows by weight of oxide: the content of the VIB group metal oxide is 9-50%, and the content of the VIII group metal oxide is 1-15%. The catalyst carrier is porous refractory oxide, such as alumina, silica, magnesia, zirconia, boron oxide, titania, etc. According to the use requirement of the catalyst, one or more of proper auxiliary agents such as fluorine, phosphorus, boron, silicon, magnesium, zirconium and the like can be added.
The high-acidity hydrogenation catalyst of the invention contains molecular sieves and/or silica-alumina components. The molecular sieve is preferably ZSM-5 and/or Y-type molecular sieve and/or beta molecular sieve. Based on the weight of the hydro-upgrading catalyst carrier, the content of the molecular sieve is 1% -15%, the content of the silicon-aluminum component is 0% -85%, the content of the aluminum oxide is 3% -99%, preferably the content of the molecular sieve is 1% -10%, the content of the silicon-aluminum component is 0% -65%, and the content of the aluminum oxide is 10% -90%.
The silicon-aluminum component refers to amorphous silicon-aluminum powder, wherein the content of silicon in terms of oxide is 10% -80%.
The high-acidity hydrogenation catalyst disclosed by the invention has the advantages that the content of the catalyst carrier is 55.0-93.5 wt%, preferably 60.0-90.0 wt%, the content of the group VIB metal oxide is 5.0-35.0 wt%, preferably 10.0-30.0 wt%, and the content of the group VIII metal oxide is 0.5-15.0 wt%, preferably 2.0-10.0 wt%, based on the weight of the catalyst.
By adopting the method, the reaction temperature is gradually increased along the direction of the reactant flow, the concentration of nickel atoms on the surface of the hydrotreating catalyst is gradually increased, and the denitrification performance of the catalyst is favorably exerted through the effect of the hydrotreating catalyst in different reaction areas. The grading filling mode of the catalyst is beneficial to improving the integral denitrification effect of the device, and is particularly suitable for the treatment process of high aromatic hydrocarbon raw materials such as boiling bed wax oil, slurry bed wax oil and the like.
Detailed Description
X-ray photoelectron spectroscopy (XPS) adopts Multilab model 2000 spectrometer produced by American thermoelectric corporation (VG), excitation source MgKα, analysis chamber vacuum degree higher than 10 -6 Pa, C1s (284.6 ev) as internal standard, and corrects nuclear power effect. TPR characterization used an AMI-200 full-automatic chemical adsorption apparatus by Altamira company, USA, 5% H 2/Ar as the reaction gas, high purity argon as the carrier gas, and a heating rate of 10deg.C/min.
The total acid amount of the surface infrared of the sample is measured by a Nicolet-560 type infrared spectrophotometer, and the pure sample is pressed into tablets, and the weight of each tablet is 20 mg. After the sample was purified at 500 ℃, it was measured by adsorption with pyridine as a probe molecule.
In the present invention, hydrotreating catalysts having different surface nickel atom concentrations may be prepared using commercially available commercial products, or by any of the existing catalyst conditioning techniques. If more nickel is introduced in the preparation of the catalyst, different inorganic or organic auxiliary agents are introduced in the preparation process of the carrier and the catalyst, the heat treatment temperature of the catalyst is changed, and the distribution of nickel atoms is improved. Taking introduction of different inorganic or organic auxiliary agents in the preparation process of the carrier and the catalyst as an example, the inorganic auxiliary agents are one or more of fluorine, silicon, phosphorus, boron, magnesium, zirconium and the like, and the organic auxiliary agents are one or more of nitrogen-containing organic compounds, sulfur-containing organic compounds and oxygen-containing organic compounds. The inorganic or organic auxiliary may be introduced at any stage, such as any stage or stages prior to, simultaneously with and subsequent to the impregnation of the group VIB and group VIII metal components. The organic additive is one or more of nitrogen-containing organic compounds, sulfur-containing organic compounds and oxygen-containing organic compounds. The organic additive may be introduced at any step, such as any step or steps prior to, simultaneously with and after impregnation of the group VIB and group VIII metal components. The types of organic additives are well known to those skilled in the art. The nitrogen-containing organic compound is an organic compound containing at least one covalent bond nitrogen atom, such as: ethanolamine, diethanolamine, triethanolamine, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and cyclohexanediamine tetraacetic acid, and the like. The sulfur-containing organic compound is an organic compound containing at least one covalent bond sulfur atom, such as mercaptan (general formula R-SH), thioether (general formula R-S-R) and disulfide (general formula R-S-S-R), wherein R in the sulfur-containing compound is an alkyl group containing 1-10 carbon atoms, such as ethanethiol, ethanepropyl sulfide, dimethyl disulfide and the like. The sulfur-containing organic compound may contain one or more substitutions of carboxyl, carbonyl, ester, ether, hydroxyl, mercapto groups, such as thioglycolic acid, mercaptopropionic acid, dimercaptopropanol, and the like. In addition to the above sulfur-containing compounds, sulfones and sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, and the like may be contained. The oxygen-containing organic compound is an organic compound containing at least one carbon atom and one oxygen atom. The oxygen containing moiety may be a carboxyl, carbonyl, hydroxyl moiety or a combination thereof. These substances may be acids such as acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, etc., alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolethane, etc., ethers such as diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, polyethylene glycol, etc., saccharides such as glucose, fructose, lactose, maltose, sucrose, etc., ketones, phenols, aldehydes, and lipids. The drying and/or calcination heat treatment temperatures also have an important effect on the concentration of nickel atoms on the surface of the hydrotreating catalyst. The surface nickel atom concentration of the hydrotreating catalyst with the same nickel element mass content is higher when the hydrotreating catalyst is treated at low temperature; the surface nickel atom concentration of the hydrotreating catalyst with the same nickel element mass content is lower when the hydrotreating catalyst is treated at high temperature. The low temperature and the high temperature are relative, the treatment temperature ranges from 80 ℃ to 700 ℃, for example, the heat treatment temperature can be defined as 80 ℃ to 300 ℃, and the treatment temperature is preferably 120 ℃ to 200 ℃ and is treated at the low temperature; the heat treatment temperature is 350 ℃ to 700 ℃, preferably 400 ℃ to 550 ℃ and is regarded as high-temperature treatment.
The following examples further illustrate the details of the present invention, but are not to be construed as limiting the invention to the examples, wherein the following examples and comparative examples are by mass percent unless otherwise specified.
The properties of the carriers used in the examples and comparative examples are shown in Table 1, and the SiO 2 content in the Si-Al component is 40%.
TABLE 1 Properties of the vectors used in examples and comparative examples
Example 1
The preparation methods of the catalysts used in the examples and comparative examples are given in this example, but the following preparation methods are not exclusive and do not limit the present invention.
The preparation method of the catalyst A comprises the following steps: the carrier Z is impregnated with the impregnating solution containing Mo and Ni in equal volume, and the catalyst is marked as A after being dried at 120 ℃ for 3 hours and baked at 500 ℃ for 2 hours.
The preparation method of the catalyst B comprises the following steps: the carrier L is impregnated with the impregnating solution containing Mo and Ni in equal volume, and the catalyst is marked as B after being dried at 120 ℃ for 3 hours and baked at 500 ℃ for 2 hours.
The preparation method of the catalyst C comprises the following steps: the carrier Z is impregnated with an impregnating solution containing Mo and Ni in an equal volume, wherein the impregnating solution contains glycol and citric acid, and the mole ratio of the glycol, the citric acid and nickel atoms is 0.5:0.5:1, dried at 120℃for 3 hours, the catalyst obtained is designated C.
The preparation method of the catalyst D comprises the following steps: the carrier Z is impregnated with an impregnating solution containing Mo and Ni in an equal volume, wherein the impregnating solution contains ethylene glycol, and the mole ratio of the ethylene glycol to nickel atoms is 0.5:1, drying at 120℃for 3 hours, and calcining at 430℃for 2 hours, the catalyst obtained was designated as D.
Table 2 main properties of the oxidation state catalyst prepared
Example 2
This example gives an evaluation of the loading scheme of the catalyst. Three reaction beds are arranged along the flow direction of the reactants, the volumes of the beds are respectively 70mL, 10mL and 20mL, and the reaction temperatures are respectively controlled to be 350 ℃, 370 ℃ and 380 ℃.
Test number S1: the three reaction beds are sequentially filled with a catalyst A, a catalyst B and a catalyst C along the flow direction of the reactants.
Test number S2: catalysts A and D (30 mL in volume of A, 40mL in volume of D) catalyst B and catalyst C were packed sequentially along the three reaction beds in the direction of the reactant stream.
Test number S3: the three reaction beds are sequentially filled with a catalyst D, a catalyst B and a catalyst C along the flow direction of the reactants.
Comparative example 1
This comparative example gives an evaluation of the loading scheme of the catalyst. Three reaction beds are arranged along the flow direction of the reactants, the volumes of the beds are respectively 70mL, 10mL and 20mL, and the reaction temperatures are respectively controlled to be 350 ℃, 370 ℃ and 380 ℃.
Test number D1: the three reaction beds are sequentially filled with a catalyst C, a catalyst B and a catalyst A along the flow direction of the reactants.
Test number D2: the three reaction beds are sequentially filled with a catalyst A, a catalyst A and a catalyst A along the flow direction of the reactants.
Test number D3: the three reaction beds are sequentially filled with a catalyst C, a catalyst C and a catalyst C along the flow direction of the reactants.
Example 3
This example is an activity evaluation experiment of the catalyst.
The catalyst activity evaluation experiment is carried out on a three-tube serial small hydrogenation device, and the catalyst is presulfided before the activity evaluation. The catalyst evaluation conditions are that the total reaction pressure is 14.0MPa, the liquid hourly space velocity is 1.0 h -1, and the hydrogen-oil volume ratio is 1200:1, the properties of the raw oil for activity evaluation experiments are shown in Table 3, and the results of activity evaluation are shown in Table 4.
TABLE 3 Properties of raw oil
Table 4600 hours catalyst Activity evaluation results
As can be seen from the evaluation results of Table 4, the catalyst system has greatly improved denitrification activity and better aromatic saturation performance compared with the comparative example, and can provide excellent feed for the hydrocracking section.
Claims (11)
1. A hydrotreating process characterized by: the method comprises the following steps: the method comprises the steps that raw oil enters a hydrogenation reaction zone, and is divided into three sections of reaction zones along the flow direction of a material flow, namely a shallow denitrification reaction zone, an isomerism-shallow cracking reaction zone and a deep denitrification reaction zone, wherein the nickel atom concentration on the surface of a hydrotreating catalyst filled in the deep denitrification reaction zone is higher than that of a hydrotreating catalyst filled in the shallow denitrification reaction zone, and the infrared total acid of the catalyst filled in the isomerism-shallow cracking reaction zone is higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone and the deep denitrification reaction zone; the reaction temperature of the shallow denitrification reaction zone is 280-380 ℃, the reaction temperature of the isomerism-shallow cracking reaction zone is 350-400 ℃, the reaction temperature of the deep denitrification reaction zone is 370-420 ℃, and the average reaction temperature of different reaction zones is sequentially increased by 10-30 ℃ in the same reaction system.
2. The method according to claim 1, characterized in that: the surface nickel atom concentration of the hydrotreating catalyst filled in the deep denitrification reaction zone is 3-80% higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone, and the infrared total acid content of the catalyst filled in the isomerism-shallow cracking reaction zone is 0.05-0.20 mmol/g higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone and the deep denitrification reaction zone.
3. The method according to claim 2, characterized in that: the nickel atom concentration of the surface of the hydrotreating catalyst filled in the deep denitrification reaction zone is 5% -30% higher than that of the surface of the hydrotreating catalyst filled in the shallow denitrification reaction zone, and the infrared total acid of the catalyst filled in the isomerism-shallow cracking reaction zone is 0.1mmol/g-0.15mmol/g higher than that of the hydrotreating catalyst filled in the shallow denitrification reaction zone and the deep denitrification reaction zone.
4. The method according to claim 1, characterized in that: the volume ratio of the catalyst filled in the shallow denitrification reaction zone, the isomerism-shallow cracking reaction zone and the deep denitrification reaction zone is 1.0-10.0: 0.2-2.0: 0.5 to 8.0.
5. The method according to claim 1, characterized in that: any reaction zone is filled with one catalyst or a plurality of catalysts, and the filling volume ratio of adjacent catalyst beds is 1:20-20:1.
6. The method according to claim 1 or 5, characterized in that: the filling volume ratio of adjacent catalyst beds for filling various catalysts is 1:10-10:1.
7. The method according to claim 1 or 5, characterized in that: the filling volume ratio of adjacent catalyst beds for filling various catalysts is 1:5-5:1.
8. The method according to claim 1, characterized in that: the main properties of the raw oil are as follows: the range of the distillation range, the initial distillation point is more than 180 ℃, and the final distillation point is less than 600 ℃; the density is 0.8000-0.9500 g cm -3 at 20 ℃; nitrogen content is 100-8000 mug.g -1; sulfur content is 0.05wt% to 5.0wt% and aromatic hydrocarbon content is 20wt% to 80wt%.
9. The method according to claim 1, characterized in that: the raw oil passes through the shallow denitrification reaction zone to reduce the nitrogen impurity content to less than 300ppm.
10. The method according to claim 1, characterized in that: any of the hydrotreating catalysts loaded in the three-stage reaction zone contains metal components of groups VIB and VIII.
11. The method according to claim 1, characterized in that: the catalyst filled in the isomerism-shallow cracking reaction zone contains molecular sieve and/or silicon-aluminum components.
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