CN104593051B - A kind of start-up method of sulfurized hydrogenation catalyst - Google Patents
A kind of start-up method of sulfurized hydrogenation catalyst Download PDFInfo
- Publication number
- CN104593051B CN104593051B CN201310532066.0A CN201310532066A CN104593051B CN 104593051 B CN104593051 B CN 104593051B CN 201310532066 A CN201310532066 A CN 201310532066A CN 104593051 B CN104593051 B CN 104593051B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- group viii
- viii metal
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002738 chelating agent Substances 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052756 noble gas Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- -1 nitrogen-containing compound Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 25
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000002161 passivation Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052976 metal sulfide Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the start-up method of a kind of sulfurized hydrogenation catalyst。The method includes: with the organic complex solution impregnation sulfurized hydrogenation catalyst of group VIII metal; then heat treatment is carried out; sulfurized hydrogenation catalyst surface is made to form layer protecting film; then introduce in the presence of an inert gas and go into operation after oil processes; switch hydrogen again; after steady air current, adjust pressure and temperature to reaction pressure and reaction temperature, enter raw oil and proceed by hydrogenation reaction。The inventive method not only can be passivated sulfide type catalyst, it is simple to the transport of catalyst, storage and filling, but also can improve the Hydrogenation of catalyst。
Description
Technical field
The present invention relates to the start-up method of a kind of sulfurized hydrogenation catalyst。
Background technology
Hydrogenation catalyst generally with refractory porous without changing oxide for carrier, such as aluminium oxide, silicon oxide, titanium oxide, zirconium oxide etc., with vib (Mo and/or W) and group VIII metal (Co and/or Ni) for active metal component。Hydrogenation catalyst is generally oxidation state before use, namely active metal exists in the form of an oxide, and the material really playing active function when actually used is metal sulfide, so needing before use by oxide, the active metal in hydrogenation catalyst is converted into sulfide。
The sulfuration of hydrogenation catalyst is divided into in-situ presulfurization and ex situ presulfiding。Wherein in-situ presulfurization is to carry out in reactor, this not only adds production cost, and human and environment is easily polluted by sulfidation。Ex situ presulfiding presses the existence of activity over catalysts metal, two kinds can be divided into: a kind of is the ex situ presulfiding of complete meaning, it is commonly referred to as sulfide type catalyst (or sulphided state catalyst), active metal in catalyst exists with highly active metal sulfide form, but sulfide type catalyst is easily spontaneous combustion in atmosphere, it is therefore necessary to be passivated；Another kind is the pre-sulfide catalyst of load sulfur type, namely the active metal in catalyst is not converted into metal sulfide, but form the intermediary of complex or oxysulfide with vulcanizing agent, such pre-sulfide catalyst in atmosphere can stable existence, after being loaded into reactor, with Hydrogen activation, sulfur oxygen bond rupture, generate highly active metal sulfide。
USP4943547, USP215954 etc. elemental sulfur is joined in high boiling oil or organic solvent previously generate suspension again with fresh catalyst effect, or use high boiling point oil-impregnated after elemental sulfur and contacts fresh catalyst。Elemental sulfur and organic sulfur are dissolved in a solvent by USP6077803, simultaneously under the existence of stabilizer, elemental sulfur are introduced catalyst。Organic solvent and elemental sulfur are introduced in oxidation state hydrogenation catalyst by CN101417230A, are then heated pretreatment under certain condition, and heat treated carries out in the presence of water vapor。The above processing method broadly falls into the technology of preparing of the pre-sulfide catalyst of load sulfur type, and active metal forms complex or oxysulfide with vulcanizing agent。Above-mentioned load sulfur type catalyst, in start-up process, has on-stream time short, and Star-up is simple, and people is endangered little, the advantages such as environmental pollution is little by refinery equipment small investment。But there is also weak point, the complex or the oxysulfide that are formed due to active metal and vulcanizing agent easily decompose under hydrogen effect, introduce the sulfuration that after hydrogen, active metal is too early at low temperatures, discharge hydrogen sulfide gas, affect the sulphidity of the airtight of device and active metal。
Sulfide type catalyst is easily spontaneous combustion in atmosphere, need to it be passivated。Generally passivating method mainly has two kinds at present, and gaseous passivation and liquid phase are passivated。
Gaseous passivation is to adopt passivating gas to be passivated, and be passivated by the active sulfide on surface, forms layer oxide film, makes internal active substance and oxygen-barrier, and the passivating gas wherein mainly used is oxygen, using noble gas as carrier gas。Catalyst after expanded bed first processes with hydrogen and hydrogen sulfide gas, is changed to the noble gas passivation of oxygen-containing 0.25 ~ 2.5%, prepares the sulfide type catalyst of complete meaning by US5958816。This catalyst does not need activation when going into operation, and can directly use, but the method makes amount of activated metal can not be fully converted to highly active activity phase mutually, can lose amount of activated component, cause the activity decrease of catalyst。
Liquid phase passivation is to introduce liquid phase passivator at sulphided state catalyst surface; catalyst surface forms one layer of organic protective film and makes itself and oxygen-barrier; prevent metal sulfide from reacting; liquid phase passivator is generally adopted to be generally heavy hydrocarbon material, such as white oil, gas oil, paraffin, animals and plants wet goods。The passivation of sulphided state catalyst disclosed in US3453217 is to prevent metal sulfide and oxygen reaction in catalyst by introducing the hydrocarbon compound of liquid in catalyst pores。Wherein the boiling point of this hydrocarbon compound is 210 ~ 649 DEG C, including virgin petroleum fractions, and particularly paraffin。Hydrogenation catalyst disclosed in CN200480018664.5, after sulfuration, adopts oxidation processes or is passivated processing with weight inert organic liquid such as gas oil and hexadecane etc.。The protecting film that this liquid-like phase passivator is formed can be removed by heating, hydrogenolysis etc. when reaction, does not affect the activity of sulphided state catalyst as far as possible。
Summary of the invention
For the deficiencies in the prior art, the invention provides the start-up method of a kind of sulfurized hydrogenation catalyst。The method not only can be passivated sulfide type catalyst, it is simple to the transport of catalyst, storage and filling, it is also possible to improves the Hydrogenation of catalyst。
The start-up method of sulfurized hydrogenation catalyst of the present invention, including:
(1) sulfurized hydrogenation catalyst is prepared；
(2) with the organic complex solution impregnation sulfurized hydrogenation catalyst of group VIII metal；Step (2) introduces group VIII metal and accounts for the 0.5% ~ 4.0% of sulfurized hydrogenation catalyst weight in oxide；
(3) catalyst of heat treatment step (2) gained；Described heat treatment is to process 1～10 hour at 80～180 DEG C；
(4) catalyst step (3) obtained loads reactor, boosts to 2～16MPa with noble gas, it is preferred to 3 ~ 8MPa, reaction bed temperature rising to 120～180 DEG C, introduces the oil that goes into operation, constant temperature is after 4 ~ 10 hours, it is continuously heating to 250～350 DEG C, constant temperature 4 ~ 10 hours；
(5) switching hydrogen, adjusts pressure and temperature after steady air current to reaction pressure and reaction temperature, enters raw oil and proceed by hydrogenation reaction。
In the inventive method, the group VIII metal described in step (2) is selected from nickel and/or cobalt, for one or more in organic acid, Organic Alcohol, ketone of the chelating agent of group VIII metal complex。Chelating agent can be selected from one or more in citric acid, lactic acid, tartaric acid, malic acid, adipic acid。Chelating agent can be selected from ethanol, propanol, butanediol one or more。Chelating agent can be selected from acetylacetone,2,4-pentanedione。Chelating agent optimization citric acid。
In the inventive method, in step (2) in the organic complex solution of group VIII metal, the concentration that group VIII metal is counted with element is for 0.5～10.0wt%。
In the inventive method, the dipping described in step (2) adopts infusion process, it is desirable to adopts and sprays method。
In the inventive method, the heat treatment described in step (3) is to process 1～10 hour at 80～180 DEG C。Wherein heat treatment can carry out under an inert gas, it is also possible to not blanketing with inert gas and carry out under air。Preferably carry out under an inert gas。Heat treatment described in step (3) makes the organic complex of group VIII metal form protecting film on sulfurized hydrogenation catalyst surface。
In the inventive method, sulfurized hydrogenation catalyst used can adopt the method for routine to prepare, it is possible to first makes oxidation state hydrogenation catalyst, then revulcanization, obtain sulfurized hydrogenation catalyst, it is also possible to be just make sulfurized hydrogenation catalyst when prepared by hydrogenation catalyst。In sulfurized hydrogenation catalyst preparation process, vulcanizing agent used can be inorganic sulfocompound or sulfur-containing organic compound。Inorganic sulfocompound is hydrogen sulfide, ammonium sulfide, elementary sulfur, thiosalt etc., and sulfur-containing organic compound is mercaptan, thioether, thiophenol, disulphide, polysulfide etc.。
Hydrogenation catalyst of the present invention, with inorganic refractory oxide for carrier, with group VIII and vib metals for active metal component, group VIII metal is selected from Ni and/or Co, and vib metals is selected from Mo and/or W。Inorganic refractory oxide is generally one or more in aluminium oxide, silicon oxide, molecular sieve。Hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or hydrocracking catalyst。With the weight of sulfurized hydrogenation catalyst for benchmark, the content that group VIII metal is counted with element is for 0.5%～12.0%, and the content that vib metals is counted with element is for 5.0%～35.0%。Can also containing adjuvant component in hydrogenation catalyst, adjuvant component is generally one or more in phosphorus, fluorine, titanium, zirconium, boron etc., and content in the catalyst is generally below 30wt%。
Noble gas used by step (4) is one or more in nitrogen, C1 ~ C4 hydro carbons etc.。
In the inventive method, the operating condition of step (5) hydrogenation reaction is: operation pressure 2.0～12.0MPa, hydrogen-oil ratio 300:1～1500:1, volume space velocity is 0.5～5.0h-1, reaction temperature 200～400 DEG C。
In the inventive method, the boiling range of the described oil that goes into operation is generally 30 ~ 350 DEG C, is selected from virgin oil。One or more in straight-run naphtha, kerosene and diesel oil that virgin oil can obtain for atmospheric and vacuum distillation unit。
In the inventive method, when described sulfurized hydrogenation catalyst is sulfurized hydrogenation Cracking catalyst, after can adopting conventional method that hydrocracking catalyst is passivated, then carry out hydrogenation reaction。The inventive method introduces the nitrogenous oil that goes into operation preferably in step (4), or in the oil that goes into operation, adds nitrogen-containing compound, such as ammonia etc.。Control the nitrogen content gone into operation in oil and be generally nitrogen content more than 0.03wt%。, it is preferred to more than 0.05wt%。
The inventive method compared with prior art, has the advantage that
(1) in the inventive method; after the organic complex dipping sulfurized hydrogenation catalyst of group VIII metal; then through heat treatment; layer of gel protecting film is formed at catalyst surface; effectively stop the aerial oxidation of catalyst; catalyst itself is absent from self-heating or inflammable problem, and institute is so that storing, transporting and filling；
(2) after the sulfurized hydrogenation catalyst after the inventive method being processed loads reactor; rising along with temperature; group VIII metal component in protecting film decomposes; and act on mutually mutually with the sulfurate activity in sulfurized hydrogenation catalyst; especially molybdenum bisuphide or tungsten disulfide; such group VIII metal forms sulfide and is dispersed in the limit of sulfurate activity phase wafer, angle, rib position and fault location, forms highly active Ni(Co)-W-S or Ni(Co)-Mo-S phase。And, the sulfide that the group VIII metal component in protecting film is formed is dispersed in catalyst surface, improves the dispersion of active metal component, is effectively improved the hydrogenation activity of catalyst。
(3) catalyst of the present invention directly heats up and goes into operation, and without exothermic phenomenon in process, saves on-stream time, environmentally friendly。
Detailed description of the invention
The technical characterstic that the invention is further illustrated by the following examples, but these embodiments can not limit the present invention。The processing method of sulfide type catalyst of the present invention illustrates for oxidation state hydrogenation catalyst。
For the feature of the present invention is described, it is raw material that embodiment and comparative example all choose the industrial hydrogenation catalyst of same batch。
Catalyst I is Hydrobon catalyst, with aluminium oxide for carrier。Catalyst II is hydrotreating catalyst, with aluminium oxide for carrier。Catalyst III is hydrocracking catalyst, and with amorphous silica-alumina and Y type molecular sieve for carrier, the content of Y type molecular sieve accounts for the 15% of catalyst weight。
Table 1
| Catalyst I | Catalyst II | Catalyst III 3--> | |
| Catalyst forms | |||
| WO3, wt% | 11.0 | - | 22.7 |
| MoO3, wt% | 5.0 | 25.0 | - |
| NiO, wt% | 3.4 | 4.0 | 6.0 |
| Character | |||
| Pore volume/mL g-1 | 0.5 | 0.34 | 0.4 |
| Specific surface area/m2·g-1 | 245 | 160 | 258 |
| Dense packing density/g cm-3 | 0.74 | 0.9 | 0.9 |
The preparation of embodiment 1 catalyst A
Take 100g oxidized catalyst I, pass into the gaseous mixture of hydrogen and hydrogen sulfide, H2:H2S=4:1, is warming up to 300 DEG C and vulcanizes 6 hours, and catalyst is taken out in cooling, obtains sulfide type catalyst。Spray with the aqueous solution of citric acid nickel (concentration counted with nickel is for 2.5g/100ml), make the citric acid nickel (in nickel oxide) of introducing account for the 0.5% of sulfide type catalyst weight, process 6 hours in lower 150 DEG C of nitrogen protection afterwards, obtain catalyst A。
Catalyst A is loaded in reactor, keep nitrogen pressure 3.4MPa, directly it is warming up to 120 DEG C, introducing straight-run diesel oil, be continuously heating to 300 DEG C, constant temperature is cooled to 280 DEG C after 6 hours, use hydrogen exchange nitrogen, swap-in raw oil simultaneously, constant temperature starts hydrogenation reaction, sample analysis after reacting 24 hours after 24 hours。Reaction condition: reaction temperature 350 DEG C, reaction pressure 3.4MPa, hydrogen-oil ratio 360, volume space velocity 2.0, its hydrodesulfurization activity is in Table 2。
The preparation of embodiment 2 catalyst B
Take 100g oxidized catalyst II, pass into hydrogen, be warming up to 120 DEG C and start into sulfurized oil, containing CS in sulfurized oil25%(v%), constant temperature is continuously heating to 230 DEG C of constant temperature and vulcanizes 3 hours after 1 hour, is warming up to 320 DEG C afterwards and vulcanizes 3 hours, and catalyst is taken out in cooling, obtains sulfide type catalyst。Spray with the aqueous solution of citric acid cobalt (concentration counted with cobalt is for 4.5g/100ml), make the citric acid cobalt (in cobalt oxide) of introducing account for the 1% of sulfide type catalyst weight, process 12 hours in lower 120 DEG C of air afterwards, obtain catalyst B。
Going into operation and reaction condition is with embodiment 1, its hydrodesulfurization activity is in Table 2。
The preparation of embodiment 3 catalyst C
Take 100g oxidized catalyst III, pass into the gaseous mixture of hydrogen and hydrogen sulfide, H2:H2S=4:1, is warming up to 300 DEG C and vulcanizes 6 hours, and catalyst is taken out in cooling, obtains sulfide type catalyst。Spray with the aqueous solution of citric acid nickel (concentration counted with nickel is for 2.5g/100ml), make the citric acid nickel (in nickel oxide) of introducing account for the 0.5% of sulfide type catalyst weight, process 6 hours in lower 150 DEG C of nitrogen protection afterwards, obtain catalyst C。
Catalyst C is loaded in reactor, airtight qualified after start recycle compressor, 4.0MPa is boosted to nitrogen, reaction bed temperature is risen to 120 DEG C, introduce coking kerosene (nitrogen content is 0.035wt%), it is continuously heating to 300 DEG C, constant temperature is cooled to 280 DEG C after 6 hours, use hydrogen exchange nitrogen, control hydrogen dividing potential drop and ensure that cracking zone bed temperature rise is less than 40 DEG C, when in high score water, ammonia density is 0.8wt%, start to warm up and rise to 320 DEG C of constant temperature and start to switch raw oil after 24 hours and react, sample analysis after reacting 24 hours。Reaction condition: reaction temperature 370 DEG C, reaction pressure 15.5MPa, hydrogen-oil ratio 1000:1, volume space velocity 1.0(provides start-up process and reaction condition), its hydrogenation cracking activity is in Table 3。
Comparative example 1
Take 100g oxidized catalyst I, pass into hydrogen, be warming up to 120 DEG C and start into sulfurized oil, containing CS in sulfurized oil25%(v%), constant temperature is continuously heating to 230 DEG C of constant temperature and vulcanizes 3 hours after 1 hour, is warming up to 300 DEG C afterwards and vulcanizes 3 hours, and swap-in raw oil rises to 350 DEG C of constant temperature and starts reaction after 6 hours afterwards, and reaction condition is with embodiment 1, and its hydrodesulfurization activity is in Table 2。
Comparative example 2
Take oxidation catalyst I, spray with the aqueous solution of citric acid nickel (concentration counted with nickel is for 2.5g/100ml), make the citric acid nickel (in nickel oxide) of introducing account for the 0.5% of catalyst weight, then drying and roasting, obtain catalyst I-1。Catalyst I-1 is carried out vulcanizing in device by the method adopting comparative example 1, and start-up process and reaction condition are with comparative example 1, and its hydrodesulfurization activity is in Table 2。
Comparative example 3
The method that oxidized catalyst in comparative example 2 adopts embodiment 1 is vulcanized, obtains sulfide type catalyst, then adopt oxygen passivation, the catalyst I-2 after being passivated。Being loaded in reactor by catalyst I-2, start-up process and reaction condition are with embodiment 1, and its hydrodesulfurization activity is in Table 2。
Comparative example 4
The method that oxidized catalyst in comparative example 2 adopts embodiment 1 is vulcanized, obtains sulfide type catalyst, then adopt paraffin hydrocarbon passivation, the catalyst I-3 after being passivated。Being loaded in reactor by catalyst I-3, start-up process and reaction condition are with embodiment 1, and its hydrodesulfurization activity is in Table 2。
Comparative example 5
Take 100g oxidized catalyst II, spray with the aqueous solution of citric acid cobalt (concentration counted with cobalt is for 4.5g/100ml), make the citric acid cobalt (in cobalt oxide) of introducing account for the 1% of sulfide type catalyst weight, then drying and roasting, obtain catalyst II-1。Catalyst II-1 is carried out vulcanizing in device by the method adopting comparative example 1, and start-up process and reaction condition are with comparative example 1, and its hydrodesulfurization activity is in Table 2。
Comparative example 6
Take oxidation catalyst III, spray with the aqueous solution of citric acid nickel (concentration counted with nickel is for 2.5g/100ml), make the citric acid nickel (in nickel oxide) of introducing account for the 0.5% of catalyst weight, then drying and roasting, obtain catalyst D。Catalyst D is loaded in reactor, passes into the gaseous mixture of hydrogen and hydrogen sulfide, H2:H2S=4:1, is warming up to 320 DEG C and vulcanizes 6 hours, reduces the inlet temperature refined with cracking zone to 200 DEG C, introduce the nitrogenous oil that goes into operation afterwards, when in high score water, ammonia density is 0.8wt%, start to warm up and rise to 320 DEG C of constant temperature and start to switch raw oil after 6 hours and react, sample analysis after reacting 24 hours。Reaction condition is with embodiment 3, and its hydrogenation cracking activity is in Table 3。
The XPS analysis of table 2 hydrofinishing and process catalyst and evaluation result
| Catalyst | Catalyst surface (Ni+Co)/Al(atomic ratio) | Desulfurization degree, wt% | Denitrification percent, wt% |
| A | 4.0 | 99.2 | >98.3 |
| B | 4.9 | 99.5 | >98.3 |
| I | 2.9 | 97.8 | 97.2 |
| I-1 | 3.3 | 98.2 | 97.5 |
| I-2 | 3.2 | 98.0 | 97.9 |
| I-3 | 3.2 | 98.1 | 97.8 |
| II-1 | 4.2 | 98.8 | 98.0 |
The XPS analysis of table 3 hydrocracking catalyst and evaluation result
| Embodiment 3 | Comparative example 6 | |
| C | D | |
| Catalyst surface Ni+Co/Al(atomic ratio) | 6.0 | 5.5 |
| Liquid is received, wt% | 98.3 | 98.1 5 --> |
| Product slates, wt% | ||
| <82℃ | 3.0 | 3.5 |
| 82～138 DEG C | 7.6 | 8.0 |
| 138～249 DEG C | 23.4 | 21.8 |
| 249～371 DEG C | 28.6 | 30.5 |
| >371℃ | 35.9 | 34.2 |
| Middle distillates oil selectivity | 82.5 | 81.0 |
Claims (19)
1. a start-up method for sulfurized hydrogenation catalyst, including:
(1) sulfurized hydrogenation catalyst is prepared；
(2) with the organic complex solution impregnation sulfurized hydrogenation catalyst of group VIII metal；Step (2) introduces group VIII metal and accounts for the 0.5%～4.0% of sulfurized hydrogenation catalyst weight in oxide；
(3) catalyst of heat treatment step (2) gained；Described heat treatment is to process 1～10 hour at 80～180 DEG C；
(4) catalyst step (3) obtained loads reactor, boosts to 2～16MPa with noble gas, reaction bed temperature rises to 120～180 DEG C, introduces the oil that goes into operation, and constant temperature, after 4～10 hours, is continuously heating to 250～350 DEG C, constant temperature 4～10 hours；
(5) switching hydrogen, adjusts pressure and temperature after steady air current to reaction pressure and reaction temperature, enters raw oil and proceed by hydrogenation reaction；
Wherein, in step (2), for one or more in organic acid, Organic Alcohol, ketone of the chelating agent of group VIII metal complex。
2. in accordance with the method for claim 1, it is characterised in that the group VIII metal described in step (2) is selected from nickel and/or cobalt。
3. in accordance with the method for claim 1, it is characterised in that in step (2), for one or more in citric acid, lactic acid, tartaric acid, malic acid, adipic acid of the chelating agent of group VIII metal complex。
4. in accordance with the method for claim 1, it is characterised in that in step (2), for the chelating agent with group VIII metal complex selected from citric acid。
5. in accordance with the method for claim 1, it is characterised in that in step (2), for the chelating agent of group VIII metal complex selected from ethanol, propanol, butanediol one or more。
6. in accordance with the method for claim 1, it is characterised in that in step (2), the chelating agent being used for group VIII metal complex is acetylacetone,2,4-pentanedione。
7. the concentration that in accordance with the method for claim 1, it is characterised in that in step (2) in the organic complex solution of group VIII metal, group VIII metal is counted with element is for 0.5wt%～10.0wt%。
8. in accordance with the method for claim 1, it is characterised in that the dipping described in step (2) adopts and sprays method。
9. in accordance with the method for claim 1, it is characterised in that the heat treatment described in step (3) carries out under an inert gas, or not blanketing with inert gas and carry out under air。
10. in accordance with the method for claim 1, it is characterised in that the heat treatment described in step (3) makes the organic complex of group VIII metal form protecting film on sulfurized hydrogenation catalyst surface。
11. in accordance with the method for claim 1, it is characterised in that described hydrogenation catalyst is Hydrobon catalyst, hydrotreating catalyst or hydrocracking catalyst。
12. the method described in claim 1 or 11, it is characterized in that described hydrogenation catalyst, with inorganic refractory oxide for carrier, with group VIII and vib metals for active metal component, group VIII metal is selected from Ni and/or Co, and vib metals is selected from Mo and/or W, with the weight of sulfurized hydrogenation catalyst for benchmark, the content that group VIII metal is counted with element is for 0.5%～12.0%, and the content that vib metals is counted with element is for 5.0%～35.0%。
13. the method described in claim 1 or 11, it is characterised in that containing adjuvant component in described hydrogenation catalyst, adjuvant component is one or more in phosphorus, fluorine, titanium, zirconium, boron, and content in the catalyst is below 30wt%。
14. in accordance with the method for claim 1, it is characterised in that the noble gas used by step (4) is one or more in nitrogen, helium, argon and C1～C4 hydro carbons。
15. in accordance with the method for claim 1, it is characterised in that in step (4), boost to 3～8MPa with noble gas。
16. in accordance with the method for claim 1, it is characterised in that the boiling range of the oil that goes into operation described in step (4) is 30～350 DEG C, selected from virgin oil。
17. in accordance with the method for claim 1, it is characterised in that when described sulfurized hydrogenation catalyst is sulfurized hydrogenation Cracking catalyst, after hydrocracking catalyst need to being passivated, then carry out hydrogenation reaction。
18. in accordance with the method for claim 17, it is characterised in that: introduce the nitrogenous oil that goes into operation in step (4), or in the oil that goes into operation, add nitrogen-containing compound, hydrocracking catalyst is passivated。
19. in accordance with the method for claim 1, it is characterised in that the operating condition of step (5) hydrogenation reaction is: operation pressure 2.0～12.0MPa, hydrogen-oil ratio 300:1～1500:1, volume space velocity is 0.5～5.0h-1, reaction temperature 200～400 DEG C。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532066.0A CN104593051B (en) | 2013-11-03 | 2013-11-03 | A kind of start-up method of sulfurized hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532066.0A CN104593051B (en) | 2013-11-03 | 2013-11-03 | A kind of start-up method of sulfurized hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104593051A CN104593051A (en) | 2015-05-06 |
| CN104593051B true CN104593051B (en) | 2016-06-22 |
Family
ID=53119123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310532066.0A Active CN104593051B (en) | 2013-11-03 | 2013-11-03 | A kind of start-up method of sulfurized hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104593051B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113117763B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Passivation method of vulcanization type hydrogenation catalyst |
| CN113509954A (en) * | 2020-04-09 | 2021-10-19 | 中国石油化工股份有限公司 | Preparation method and application of passivated sulfuration-state hydrocracking catalyst |
| CN114437766B (en) * | 2020-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Diesel oil hydrogenation start-up method using semi-vulcanization catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07108173A (en) * | 1993-10-15 | 1995-04-25 | Idemitsu Kosan Co Ltd | Impregnation liquid for producing hydrogenation catalyst, method for producing hydrogenation catalyst, and method for hydrotreating hydrocarbon oil |
| CN102443412A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for starting up ex-situ presulfurization class II active center hydrogenation catalyst |
| CN103100446A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of hydrogenation unit |
-
2013
- 2013-11-03 CN CN201310532066.0A patent/CN104593051B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07108173A (en) * | 1993-10-15 | 1995-04-25 | Idemitsu Kosan Co Ltd | Impregnation liquid for producing hydrogenation catalyst, method for producing hydrogenation catalyst, and method for hydrotreating hydrocarbon oil |
| CN102443412A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for starting up ex-situ presulfurization class II active center hydrogenation catalyst |
| CN103100446A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of hydrogenation unit |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104593051A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104593050B (en) | The start-up method of sulfurized hydrogenation catalyst | |
| CN104588043B (en) | A kind of processing method of sulfurized hydrogenation catalyst | |
| CN104117362B (en) | A kind of catalyst and preparation method of raising NiMo diesel oil hydrofining catalyst hydrogenation activities | |
| CN107456974B (en) | Hydrogenation catalyst, pretreatment method thereof, method for improving desulfurization activity of hydrogenation catalyst and application | |
| CN101992131A (en) | Method for regenerating hydrogenation catalyst, regenerated hydrogenation catalyst and application thereof | |
| CN103773436A (en) | Start-up method for ex-situ prevulcanization secondary activity center hydrogenation catalyst | |
| CN110573251A (en) | Method for adding organic compounds to porous solids in the gas phase | |
| CN109772368B (en) | High-activity hydrodesulfurization catalyst and preparation method thereof | |
| CN100360236C (en) | Treatment method before application of hydrogenation catalyst | |
| CN104593051B (en) | A kind of start-up method of sulfurized hydrogenation catalyst | |
| CN103071508B (en) | Catalyst and preparation method and application thereof, and hydrorefining method | |
| CN110479313A (en) | Hydrogenation catalyst and its preparation method and application and the method for hydrofinishing | |
| CN109772388B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN107457006A (en) | A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved | |
| CN101590437A (en) | External presulfurization method of hydrogenation catalyst | |
| CN109926100B (en) | Startup method of vulcanized hydrogenation catalyst | |
| CN105582963B (en) | A kind of preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline | |
| CN102019209B (en) | Hydrocarbon processing catalysts is carried out the method for sulfuration | |
| CN113856694B (en) | Sulfurized hydrogenation catalyst, and preparation method and application thereof | |
| CN102019210B (en) | Hydrocarbon processing catalysts is carried out the method for sulfuration | |
| CN100448542C (en) | A kind of presulfurization method of hydrogenation catalyst | |
| CN112295575B (en) | A method for preparing a hydrogenation catalyst and a method for starting a hydrogenation device | |
| CN111068794B (en) | External presulfurization method of hydrogenation catalyst | |
| CN110479300B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for hydrorefining | |
| EP2988870B1 (en) | Preparation of a sulphided catalyst and process using said catalyst for hydrotreating a sulphur-containing hydrocarbon feedstock |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |