CN114437766A - Diesel hydrogenation startup method using semi-sulfided catalyst - Google Patents
Diesel hydrogenation startup method using semi-sulfided catalyst Download PDFInfo
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- CN114437766A CN114437766A CN202011198551.5A CN202011198551A CN114437766A CN 114437766 A CN114437766 A CN 114437766A CN 202011198551 A CN202011198551 A CN 202011198551A CN 114437766 A CN114437766 A CN 114437766A
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- hydrogenation
- catalyst
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- diesel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004073 vulcanization Methods 0.000 claims abstract description 45
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000002283 diesel fuel Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000005486 sulfidation Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- -1 VIB group metals Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/24—Starting-up hydrotreatment operations
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—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
- 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
- B01J37/08—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
A diesel oil hydrogenation start-up method using a semi-vulcanized catalyst comprises the following steps: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas phase hydrogenation reaction, filling a semi-vulcanized catalyst into the hydrogenation reactor, circulating a reaction product of the gas phase hydrogenation to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanized catalyst by using hydrogen sulfide in the product until the vulcanization is finished, and stopping the circulation of the gas phase hydrogenation reaction product; the semi-sulfiding catalyst comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide and VIII group metal oxide. According to the invention, the semi-vulcanized catalyst is not subjected to a separate vulcanization process, but the materials of the reaction product in the start-up stage are recycled, and the hydrogen sulfide in the semi-vulcanized catalyst is utilized to carry out vulcanization treatment, so that the effective utilization of harmful substances is realized, the conditions in the vulcanization process are mild, and the reduction of the activity of the catalyst caused by overhigh local temperature in the vulcanization process is effectively inhibited.
Description
Technical Field
The invention relates to a diesel hydrogenation process, in particular to a diesel hydrogenation start-up method using a semi-vulcanized catalyst.
Background
The diesel hydrogenation catalyst generally needs to be subjected to vulcanization treatment under certain conditions, generally wet vulcanization and dry vulcanization are carried out, and the problems of temperature runaway, hydrogen sulfide leakage and the like easily occur in the vulcanization process of the catalyst.
CN106669860A discloses a vulcanization startup method of a hydrodesulfurization catalyst, which comprises the following steps: (1) the reactor is filled with an oxidation state hydrodesulfurization catalyst with a second type active center; (2) the device is dried by a catalyst, sealed by nitrogen, replaced by hydrogen and sealed by hydrogen; (3) introducing vulcanized oil into the reactor, and wetting the catalyst bed layer; (4) adjusting the temperature of the catalyst bed layer, and replacing with vulcanized oil I; after hydrogen sulfide penetrates through the catalyst bed layer, raising the temperature of the catalyst bed layer to 180-240 ℃, and keeping the temperature for 4-16 hours; (5) changing into vulcanized oil II, washing the bed for 4-10 h, raising the temperature of the catalyst bed to 250-330 ℃, and keeping the temperature for 4-16 h; (6) after the vulcanization is finished, the technological conditions of the system are adjusted to the reaction conditions, and the raw oil is switched to carry out normal operation. The catalyst is an oxidation state catalyst, the active component is VIB group and/or VIII group metal oxide, and the metal sulfide with hydrodesulfurization activity needs to be converted by sulfurization treatment. The group VIB metal oxides are harder to vulcanize than the group VIII metal oxides, which leads to the first vulcanization of the group VIII metal and the subsequent vulcanization of the group VIB metal in the active metal, resulting in a reduction in the number of high active centers. In addition, the vulcanization process of the invention is complex, and the problems of temperature runaway, hydrogen sulfide leakage and the like are easy to occur in the vulcanization process.
CN105709859A discloses a method for sulfurizing a fixed bed hydrogenation catalyst. And a plurality of catalyst bed layers in the hydrogenation reactor are all provided with a cold hydrogen box, and the catalyst bed layers are gradually vulcanized from top to bottom by controlling the circulating hydrogen carrying vulcanizing agent through adjusting a control valve of a cold hydrogen pipeline of each catalyst bed layer. According to the invention, the cold hydrogen boxes are arranged between the reactor beds, so that the cost of a refinery is increased, and the problems of temperature runaway, hydrogen sulfide leakage and the like are easily caused in the vulcanization method.
Disclosure of Invention
Aiming at the problems of complex vulcanization and reaction condition switching adjustment, poor vulcanization effect and bed temperature runaway at the initial stage of hydrogenation reaction in diesel hydrogenation in the prior art, the invention provides a diesel hydrogenation start-up method using a semi-vulcanized catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a diesel oil hydrogenation start-up method using a semi-vulcanized catalyst comprises the following steps: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas phase hydrogenation reaction, filling a semi-vulcanized catalyst into the hydrogenation reactor, circulating a reaction product of the gas phase hydrogenation to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanized catalyst by using hydrogen sulfide in the product until the vulcanization is finished, and stopping the circulation of the gas phase hydrogenation reaction product;
the semi-sulfiding catalyst comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide and VIII group metal oxide.
Further, the VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni.
Further, the raw material diesel oil is one or more of straight-run diesel oil, coking diesel oil and catalytic diesel oil.
Further, the sulfuration is completed under the condition that the sulfur content in the liquid phase product is less than 10ppm and the nitrogen content is less than 2.0 ppm.
Further, the reaction conditions in the hydrogenation reactor in the start-up stage are as follows: the reaction temperature is 320 ℃ and 390 ℃, and the reaction pressure is 5.0-10.0 MPa.
Further, the above semi-sulfided catalyst has a group VIB metal sulfide content of 2.2wt% to 33wt%, preferably 10wt% to 20wt%, and a group VIII metal oxide content of 0.2wt% to 12wt%, preferably 3wt% to 6wt%, based on the total weight of the catalyst.
Further, the carrier of the semi-sulfided catalyst is a porous inorganic refractory oxide, more specifically, one or more selected from the group consisting of silica, alumina, magnesia, zirconia, titania, silica alumina, silica magnesia and alumina-magnesia, and most preferably alumina. The carrier can be modified according to the needs, for example, B, P, F and other modifying elements are used for modification, and the weight percentage of the modifying elements is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier.
Further, the semi-sulfided catalyst is prepared by the following method:
(1) impregnating the carrier with an impregnating solution containing VIB group metals, drying and vulcanizing;
(2) and (2) impregnating the product obtained in the step (1) with an impregnating solution containing VIII group metals, and then drying and roasting the impregnated product in an inert atmosphere to obtain the semi-vulcanized catalyst.
Further, in the preparation method of the semi-sulfided catalyst, the preparation method of the group VIB metal impregnation solution in the step (1) is well known to those skilled in the art, for example, a phosphate or ammonium salt solution is generally adopted, the mass concentration of the impregnation solution is 0.1 g/mL-2.0 g/mL, and an equal-volume impregnation mode can be adopted. The drying conditions are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours. The vulcanization treatment is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.
Further, in the preparation method of the semi-sulfided catalyst, the preparation method of the impregnation solution of the group VIII metal in the step (2) is well known to those skilled in the art, and for example, nitrate, acetate, sulfate solution and the like are generally adopted, and the mass concentration of the impregnation solution is 0.1g/mL to 1.0g/mL, and an equal volume impregnation mode can be adopted. The inert atmosphere is N2And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.
Further, in the start-up method, after the vulcanization is completed, the circulation of the gas-phase hydrogenation reaction product is stopped, the gas-liquid separation is performed on the gas-phase hydrogenation reaction product, and a gas-phase product and a liquid-phase product are separated; the gas phase product can be recycled to the inlet of the reactor to recycle the hydrogen therein after desulfurization and denitrification, and the hydrogenation reaction is carried out again, and the liquid phase product is refined diesel oil.
Compared with the prior art, the invention has the following advantages:
(1) the semi-sulfidation catalyst is applied to the gas phase hydrogenation process of diesel oil, a separate sulfidation process is not carried out, but the materials of reaction products in the start-up stage are circulated, and the hydrogen sulfide in the semi-sulfidation catalyst is used for sulfidation treatment, so that the effective utilization of undesirable substances is realized, the conditions in the sulfidation process are mild, and the reduction of the activity of the catalyst caused by overhigh local temperature in the sulfidation process is effectively inhibited.
(2) The startup method of the invention does not need switching between the vulcanization process and the hydrogenation reaction process, thereby preventing the temperature runaway of the device in the vulcanization process, enabling the reaction of the semi-vulcanization catalyst with lower initial activity to be relatively mild, reducing the temperature rise of the gas phase reaction to a certain extent, and reducing the operation risk of the device.
(3) According to the semi-vulcanized catalyst, through the modes of dipping and vulcanizing different active metals step by step, the VIB group metal is firstly dipped on the carrier and is vulcanized in advance, and then the VIII group metal is dipped, so that the VIII group metal can cover the surface of the VIB group metal in a vulcanized state, the function of the VIII group metal auxiliary agent is fully exerted, the condition of interaction between the VIII group metal auxiliary agent and the VIB group metal is created, the generation of II type active centers is promoted, and the catalyst has higher activity after being completely vulcanized when in use.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Semi-sulfided catalysts were prepared in examples 1-4:
example 1
Adjusting the solution with ammonia water until ammonium molybdate is completely dissolved, then impregnating the alumina carrier with the same volume, and drying the alumina carrier for 3 hours at 130 ℃. Then using a catalyst containing 1.5% H2Sulfurizing S hydrogen at 320 deg.C under 4.6MPa for 10 hr, and adding N2And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving cobalt nitrate in deionized water under N2Impregnating the catalyst precursor with equal volume in the atmosphere, and then carrying out N2Drying at 90 ℃ for 4h under the atmosphere, and roasting at 320 ℃ for 3h to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: 17.8 percent of molybdenum sulfide, 4.3 percent of cobalt oxide and the balance of carrier.
Example 2
Dissolving ammonium heptamolybdate into deionized water, then soaking the solution into a phosphorus-modified alumina carrier in an equal volume, and drying the solution for 2 hours at 150 ℃. Then using a catalyst containing 3.0% CS2Carrying out vulcanization treatment on the aviation keroseneThe temperature is 360 ℃, the vulcanization pressure is 5.4MPa, the vulcanization time is 13h, and then the reaction is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving nickel nitrate in deionized water in N2Impregnating the catalyst precursor with equal volume in the atmosphere, and then carrying out N2Drying at 110 ℃ for 4h in the atmosphere, and roasting at 350 ℃ for 3h to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: 18.2% of molybdenum sulfide, 4.6% of nickel oxide and the balance of carrier.
Example 3
Dissolving ammonium metatungstate into deionized water, then soaking the solution into a boron-modified alumina carrier in the same volume, and drying the solution for 3 hours at 160 ℃. Then using a catalyst containing 3.0% CS2The aviation kerosene is subjected to vulcanization treatment, the vulcanization temperature is 350 ℃, the vulcanization pressure is 6.4MPa, the vulcanization time is 12h, and then the vulcanization is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving nickel nitrate in deionized water in N2Impregnating the catalyst precursor with equal volume in the atmosphere, and then carrying out N2Drying at 120 ℃ for 4h in the atmosphere, and roasting at 320 ℃ for 3h to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: 19.2 percent of tungsten sulfide, 3.6 percent of nickel oxide and the balance of carrier.
Example 4
Dissolving ammonium metatungstate into deionized water, then soaking the solution into a boron-modified alumina carrier in the same volume, and drying the solution for 3 hours at 120 ℃. Then using a catalyst containing 3.0% CS2The aviation kerosene is vulcanized, the vulcanization temperature is 300 ℃, the vulcanization pressure is 6.4MPa, the vulcanization time is 16h, and then the vulcanization is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving cobalt nitrate in deionized water under N2Impregnating the catalyst precursor with equal volume in the atmosphere, and then carrying out N2Drying at 110 ℃ for 4h in the atmosphere, and roasting at 350 ℃ for 3h to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: 18.5 percent of tungsten sulfide, 4.2 percent of cobalt oxide and the balance of carrier.
Comparative example 1
Dissolving ammonium metatungstate in deionized water, then soaking the solution in an alumina carrier in the same volume, drying the solution at 120 ℃ for 3 hours, and then roasting the solution at 360 ℃ for 3 hours to obtain a catalyst precursor. Dissolving cobalt nitrate into deionized water, soaking the cobalt nitrate into a catalyst precursor in the same volume, drying the cobalt nitrate at 120 ℃ for 4 hours, and roasting the cobalt nitrate at 330 ℃ for 4 hours to obtain the catalyst CS-1.
The catalyst CS-1 comprises the following components in percentage by weight: 18.5 percent of tungsten oxide, 4.2 percent of cobalt oxide and the balance of carrier.
Comparative example 2
And (2) dissolving phosphomolybdic acid and nickel nitrate into deionized water, then soaking the solution into an alumina carrier in the same volume, drying the solution at 150 ℃ for 3 hours, and then roasting the solution at 360 ℃ for 3 hours to obtain the catalyst CS-2.
The catalyst CS-2 comprises the following components in percentage by weight: 17.8 percent of molybdenum oxide, 4.6 percent of nickel oxide and the balance of carrier.
Example 5
The catalysts prepared in the above examples and comparative examples were subjected to a gas phase hydrogenation reaction:
the adopted evaluation raw oil is mixed diesel oil provided by a certain refinery of China petrochemistry, the sulfur content of the raw oil is 13000-14000 mu g/g, and the nitrogen content is 300-600 mu g/g.
The performance evaluation of hydrodesulfurization and denitrification reactions was carried out on the catalysts C-1 to C-4 and the comparative examples CS-1 to CS-2, respectively, using a 200mL fixed bed gas phase hydrogenation apparatus.
Reaction conditions of the catalyst: the mixed diesel oil is used at the airspeed of 1.5h-1Pre-sulfurizing the catalyst at 350 deg.c and hydrogen-oil volume ratio of 500 to 1 under 7.0MPa, circulating the reaction product to the inlet of the reactor, and sulfurizing the catalyst with hydrogen sulfide produced in the reactant until the liquid phase product has sulfur content less than 10 microgram/g and nitrogen content less than 2.0 microgram/g. Then stopping the circulation of the gas-phase hydrogenation reaction product, carrying out gas-liquid separation on the product, and separating a gas-phase product and a liquid-phase product; and the gas-phase product is subjected to desulfurization and denitrification and then is recycled to the inlet of the reactor to recycle the hydrogen therein, and the hydrogenation reaction is carried out again, wherein the liquid-phase product is refined diesel oil. Measuring various indexes of the refined diesel oil and calculating the desulfurization rateAnd demonomerization rate, the results are shown in table 1.
Table 1.
Claims (11)
1. A diesel oil hydrogenation start-up method using a semi-vulcanized catalyst comprises the following steps: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas phase hydrogenation reaction, filling a semi-vulcanized catalyst into the hydrogenation reactor, circulating a reaction product of the gas phase hydrogenation to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanized catalyst by using hydrogen sulfide in the product until the vulcanization is finished, and stopping the circulation of the gas phase hydrogenation reaction product;
the semi-sulfiding catalyst comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide and VIII group metal oxide.
2. The diesel fuel hydroprocessing method of claim 1, wherein the group VIB metal is Mo and/or W, and the group VIII metal is Co and/or Ni.
3. The diesel hydrogenation start-up method according to claim 1, wherein the raw diesel is one or more of straight-run diesel, coker diesel and catalyst diesel.
4. The diesel hydro-start-up method of claim 1 wherein the conditions for completion of the sulfidation are such that the liquid product has less than 10ppm sulfur and less than 2.0ppm nitrogen.
5. The diesel hydrogenation start-up method according to claim 1, wherein the reaction conditions in the hydrogenation reactor in the start-up stage are as follows: the reaction temperature is 320 ℃ and 390 ℃, and the reaction pressure is 5.0-10.0 MPa.
6. The diesel fuel hydroprocessing method of claim 1, wherein the amount of the group VIB metal sulfide in the semi-sulfided catalyst is 2.2wt% to 33wt%, preferably 10wt% to 20wt%, and the amount of the group VIII metal oxide is 0.2wt% to 12wt%, preferably 3wt% to 6wt%, based on the total weight of the catalyst.
7. The diesel fuel hydrogenation start-up method according to claim 1, wherein the carrier of the semi-sulfided catalyst is selected from one or more of silica, alumina, magnesia, zirconia, titania, silica alumina, silica magnesia and alumina-magnesia.
8. The diesel hydro-start-up method of claim 1, wherein the semi-sulfided catalyst is prepared by:
(1) impregnating the carrier with an impregnating solution containing VIB group metals, drying and vulcanizing;
(2) and (2) impregnating the product obtained in the step (1) with an impregnating solution containing VIII group metals, and then drying and roasting the impregnated product in an inert atmosphere to obtain the semi-vulcanized catalyst.
9. The diesel oil hydrogenation start-up method according to claim 8, characterized in that the group VIB metal impregnation solution in step (1) is a phosphate or ammonium salt solution, and the mass concentration of the impregnation solution is 0.1-2.0 g/mL.
10. The diesel oil hydrogenation startup method according to claim 8, wherein the impregnation solution of the group VIII metal in the step (2) is a nitrate, acetate or sulfate solution, and the mass concentration of the impregnation solution is 0.1 g/mL-1.0 g/mL.
11. The diesel hydrogenation startup method according to claim 1, wherein after completion of the vulcanization, the circulation of the product of the gas-phase hydrogenation reaction is stopped, and gas-liquid separation is performed to separate a gas-phase product and a liquid-phase product; and the gas-phase product is subjected to desulfurization and denitrification and then is recycled to the inlet of the reactor to recycle the hydrogen therein, and the hydrogenation reaction is carried out again, wherein the liquid-phase product is refined diesel oil.
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| CN102041043A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for processing vulcanized hydrogenation catalyst |
| CN103059968A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Vulcanization startup method of hydrocracking device |
| CN104593051A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | startup method of sulfuration type hydrogenation catalyst |
| CN104593050A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Operating method for vulcanized hydrogenation catalyst |
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| CN102041043A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for processing vulcanized hydrogenation catalyst |
| CN103059968A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Vulcanization startup method of hydrocracking device |
| CN104593051A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | startup method of sulfuration type hydrogenation catalyst |
| CN104593050A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Operating method for vulcanized hydrogenation catalyst |
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