CN112705225A - Oil silicon capturing agent and preparation method thereof - Google Patents
Oil silicon capturing agent and preparation method thereof Download PDFInfo
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- CN112705225A CN112705225A CN201911020775.4A CN201911020775A CN112705225A CN 112705225 A CN112705225 A CN 112705225A CN 201911020775 A CN201911020775 A CN 201911020775A CN 112705225 A CN112705225 A CN 112705225A
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- silicon
- group metal
- vulcanization
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- oil
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 61
- 239000003921 oil Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 238000004939 coking Methods 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- -1 VIB group metal oxide Chemical class 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000002283 diesel fuel Substances 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 12
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 6
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 claims description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims 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 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000010183 spectrum analysis Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 23
- 239000011265 semifinished product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 8
- 229940078494 nickel acetate Drugs 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an oil silicon capturing agent and a preparation method thereof. The oil product silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide; based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.1-12.2 wt%, the VIB group metal oxide accounts for 0.5-17.2 wt%, the VIII group metal oxide accounts for 0.1-9.0 wt%, and the carrier accounts for 61.6-90.3%. The preparation method comprises the following steps: (1) impregnating silicon catching agent carrier with impregnation liquor containing VIII group metal, drying, and making sulfur treatmentChemical treatment; (2) by containing groups VIB and
Description
Technical Field
The invention relates to a silicon capturing agent for coking naphtha and a preparation method thereof.
Background
The coking naphtha hydrofining technology can remove or partially remove impurities such as silicon, olefin, sulfur, nitrogen, aromatic hydrocarbon and the like in the raw materials, and the products can be used as fuel gasoline and chemical raw materials. The implementation of this technology can convert low value coker naphtha to high value added products.
Coker naphtha contains a significant amount of silicon which deposits on the hydrofinishing catalyst, causing catalyst deactivation. In order to slow down or avoid silicon poisoning deactivation of the hydrofinishing catalyst, the inlet portion of the reactor is typically filled with a silicon capture agent.
The development direction of the silicon capturing agent is to improve the desiliconization capability and the silicon containing capability.
CN101343565A discloses a hydrofining method of silicon-containing distillate oil. The hydrogenation catalyst with the silicon capturing function has larger pore volume and specific surface area and relatively lower metal content. CN102051202A discloses a coking naphtha silicon capturing agent and application thereof. The silicon capturing agent takes alumina as a carrier, silicon dioxide as an auxiliary agent and W, Mo and Ni as hydrogenation components. CN103920524A discloses a desiliconization agent and a preparation method and application thereof. The desiliconization agent contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier is pseudo-boehmite and a mesoporous Y-type molecular sieve. The improvement of the silicon capturing agent of the above patent is mainly focused on the carrier, and the improvement of the active component of the catalyst is less involved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an oil silicon capturing agent and a preparation method thereof. The active components in the silicon capturing agent have higher activity and better silicon containing capacity, and are suitable for the desiliconization and silicon capturing treatment of silicon-containing oil products such as coking dry gas, coking naphtha, coking diesel oil and the like.
The oil product silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide, wherein the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni; the weight of the VIII group metal sulfide is 0.1-12.2 wt%, preferably 0.4-6.8 wt% based on the total weight of the silicon capturing agent; group VIB metal oxides from 0.5wt% to 17.2wt%, preferably from 1.6wt% to 9.3 wt%; 0.1wt% to 9.0wt%, preferably 0.2wt% to 2.0wt%, calculated as group VIII metal oxide; the carrier is 61.6% -90.3%.
The silicon capturing agent is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar ratio of the +4 valence VIB group metal content to the total VIB group metal content is 70-100%. Typical vulcanization process conditions are: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more 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.
The carrier is a porous inorganic refractory oxide, is selected from one or more oxides of elements in II group, III group, IV group and IVB group of the periodic table, is more preferably selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide and aluminum magnesium oxide, and is further preferably aluminum oxide. The silicon capturing agent carrier can be modified according to the requirement, for example, modification elements such as B, P, F are adopted for modification, and the weight percentage of the modification elements is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier. The silicon capturing agent carrier can also partially adopt other crushed catalyst powder, such as a hydrocracking catalyst containing silicon oxide and a hydrocracking catalyst containing a molecular sieve.
The preparation method of the oil silicon capturing agent comprises the following steps:
(1) dipping the silicon catching agent carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material;
(2) by containing groups VIB and
and (3) dipping the vulcanized material obtained in the step (1) in a dipping solution of the group metal, and then drying and roasting the dipped material in an inert atmosphere to obtain the oil silicon catching agent.
In the method of the present invention, the preparation method of the impregnation solution of the group VIII metal in step (1) is well known to those skilled in the art, and for example, ammonium molybdate, ammonium metatungstate solution, etc. can be used, and an equal volume impregnation or other impregnation method can be used. The first mentioned
The group metals are preferably Ni and/or Co.
In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.
In the method of the present invention, the vulcanization treatment in step (1) 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 or n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 hours.
In the process of the present invention, the groups VIB and VIB in step (2) are
The preparation method of the impregnation solution of the group metals is well known to those skilled in the art, and if nitrate, acetate, sulfate solution and the like are generally adopted, equal volume impregnation or other impregnation methods can be adopted, wherein the group VIB metal is preferably Mo and/or W, and the second group VIB metal is preferably Mo and/or W
The group metals are preferably Ni and/or Co.
In the method of the invention, the inert atmosphere in the step (2) 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.
The oil silicon capturing agent is applied to the processes of coking dry gas hydrogenation, coking naphtha hydrogenation, reforming prehydrogenation, coking diesel oil hydrogenation and the like.
The oil silicon capturing agent of the invention needs to be vulcanized before application, and the general vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more 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 hours.
The traditional catalyst exists in an oxidation state before vulcanization, the edges, corners and edges of a carrier of the traditional catalyst are fewer, the oxidation state active components on the catalyst correspondingly have fewer edges, corners and edges after being converted into a vulcanization state through a vulcanization process, an active phase wafer is larger, the metal utilization rate is lower, and the reaction activity is lower. The inventor develops a new method, by the way of dipping and vulcanizing different active metals step by step, firstly dipping the VIII family metal on the carrier and vulcanizing in advance, and then dipping the VIB family and the VIB family on the sulfide
A group metal. Stepwise impregnationCan make the first
Group metal sulfides are distributed on the surface of the alumina carrier, so that the number of edges, corners and edge positions is increased, and a smaller active phase wafer is formed in the vulcanization stage of the next-step dipped VIB group metal in the start-up process; the VIII group elements in the second dipping process can disperse the VIB group elements in the dipping process, so that the size of the active phase wafer is further reduced, and the activity of the silicon capturing agent is further improved. The silicon capturing agent can reduce the quantity of active components, increase the pore volume and the specific surface area of a finished catalyst product and improve the desiliconization and silicon capturing performances of the finished catalyst product due to the improvement of the performance of the active components.
Detailed Description
The method has the characteristics that the desilication and silicon capturing performance of the silicon capturing agent is enhanced by improving the utilization rate of the hydrogenation component, the hydrogenation component with lower content is used, and higher specific surface area and pore volume are reserved.
The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The catalyst composition provided by the invention is characterized by inductively coupled plasma ICP, a transmission electron microscope and XPS energy spectrum. The catalyst provided by the invention has metal vulcanization degree of Mo4+Or W4+The content represents the degree of metal sulfidation of the catalyst. Using 30mL/min of H at 320 DEG C2S sulfurizing for 2h, characterizing the metal valence state of the surface of the sample by an XPS PEAK spectrometer, respectively fitting and peak-splitting Mo3d, W4f, Co2p and Ni2p energy spectrums by adopting XPS PEAK version4.0, and calculating according to the peak area to obtain the metal sulfurization degree. Using 30mL/min of H at 320 DEG C2S sulfurizing for 2h, and characterizing the morphology of the active phase of the sample by a transmission electron microscope, wherein the morphology is 10000nm2WS in the above area2/MoS2And (4) counting the average lamellar length and the average stacking layer number.
Example 1
An alumina support was immersed in an equal volume of an aqueous solution of cobalt nitrate so that the CoO content of the primary semifinished product was 0.3% (using as a standard analysis after calcination at 470 ℃ C.), and then dried at 100 ℃ for 3 hours to obtain a primary semifinished product A1. Then adopting dry method to sulfurSulfurizing A1 to convert the metal into Co9S8And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 260 ℃ and under the pressure of 3.7MPa to obtain a semi-finished product A2. Under the protection of nitrogen, adopting mixed aqueous solution of ammonium molybdate and cobalt nitrate to perform equal-volume impregnation on A2, so that MoO is newly added in the latter35.0% (using 470 ℃ roasting analysis as standard) and CoO 0.6% (using 470 ℃ roasting analysis as standard), drying at 85 deg.C for 5 hr under nitrogen atmosphere, and roasting at 340 deg.C for 3 hr to obtain Co9S8-MoO3-CoO/Al2O3Catalyst a 3.
Example 2
An equal volume of aqueous nickel nitrate solution was impregnated onto the alumina support to give a 1.7% NiO content on the first-stage semifinished product (using 470 ℃ roasting analysis as a standard), and then dried at 150 ℃ for 4 hours to give a first-stage semifinished product B1. Then vulcanizing B1 by dry vulcanization to convert the metal into Ni2S3And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 300 ℃ and under the pressure of 4.1MPa to obtain a semi-finished product B2. Under the protection of nitrogen, a mixed aqueous solution of ammonium molybdate and nickel nitrate is adopted to perform equal-volume impregnation on B2, so that MoO is newly added to the latter3The content of 7.0 percent (taking the analysis after roasting at 470 ℃ as a standard) and the content of NiO 0.3 percent (taking the analysis after roasting at 470 ℃ as a standard), then drying for 5 hours at 85 ℃ in a nitrogen atmosphere, roasting for 3 hours at 340 ℃ to obtain Ni2S3-MoO3-NiO/Al2O3Catalyst B3.
Example 3
An equal volume of aqueous nickel nitrate solution was impregnated onto the alumina support to give a first-stage semi-finished product with a NiO content of 3.1% (using 470 ℃ C. as a standard for post-calcination analysis), and then dried at 190 ℃ for 3 hours to give a first-stage semi-finished product C1. Then sulfurizing C1 by dry sulfurization to convert the metal into Ni2S3And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 390 ℃ under the condition of 6.3MPa to obtain a semi-finished product C2. Under the protection of nitrogen, C2 is soaked in a mixed aqueous solution of ammonium molybdate and nickel acetate in an equal volume, so that MoO is newly added in the mixed aqueous solution3The content of the extract is 17.0% (at 470 deg.C)Analysis after roasting is standard) and NiO content is 1.9 percent (analysis after roasting at 470 ℃ is standard), then drying for 5 hours at 85 ℃ in nitrogen atmosphere, roasting for 3 hours at 340 ℃ to obtain Ni2S3-MoO3-NiO/Al2O3Catalyst C3.
Example 4
In SiO2A siliceous alumina support containing 4.6% was isovolumetrically impregnated with an aqueous nickel nitrate solution to give a primary semi-finished product having a NiO content of 5.6% (using a 470 ℃ roasting analysis as a standard), and then dried at 180 ℃ for 3 hours to give a primary semi-finished product D1. Then D1 is vulcanized by dry vulcanization to convert the metal into Ni2S3And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 360 ℃ under the condition of 5.0MPa to obtain a semi-finished product D2. Under the protection of nitrogen, D2 was impregnated with a mixed aqueous solution of ammonium molybdate and cobalt nitrate in equal volume, so that the latter was newly added with MoO315.0% (using 470 ℃ roasting analysis as standard) and 2.5% (using 470 ℃ roasting analysis as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, roasting at 340 ℃ for 3 hours to obtain Ni2S3-MoO3-CoO/Al2O3-SiO2Catalyst D3.
Example 5
In SiO2The siliceous alumina carrier with a content of 7.3% was immersed in an aqueous nickel acetate solution in equal volume so that the NiO content on the primary semifinished product was 8.0% (using the analysis after calcination at 470 ℃ as a standard), and then dried at 160 ℃ for 3 hours to obtain a primary semifinished product E1. Then sulfurizing E1 by dry sulfurization to convert the metal into Ni2S3And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 350 ℃ and under the condition of 4.9MPa to obtain a semi-finished product E2. Under the protection of nitrogen, E2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium metatungstate and nickel acetate, so that WO is newly added to the E2313.0% (taking analysis after roasting at 470 ℃ as a standard) and 4.0% of NiO (taking analysis after roasting at 470 ℃ as a standard), drying at 85 ℃ for 5 hours in a nitrogen atmosphere, and roasting at 340 ℃ for 3 hours to obtain Ni2S3-WO3-NiO/Al2O3-SiO2Catalyst E3.
Example 6
In SiO2The siliceous alumina support with a content of 3.3% was immersed in an aqueous nickel acetate solution in equal volume so that the NiO content on the primary semifinished product was 11.0% (using the analysis after calcination at 470 ℃ as a standard), and then dried at 170 ℃ for 4 hours to obtain a primary semifinished product F1. Then F1 is vulcanized by dry vulcanization to convert the metal into Ni2S3And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 330 ℃ under the condition of 4.2MPa to obtain a semi-finished product F2. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium metatungstate and nickel acetate to perform equal-volume impregnation on F2, so that the later is added with WO310.0% (using 470 ℃ roasting analysis as standard) and NiO content 8.0% (using 470 ℃ roasting analysis as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, roasting at 340 ℃ for 3 hours to obtain Ni2S3-WO3-NiO/Al2O3-SiO2Catalyst F3.
Example 7
Mixing 12% of mixed hydrocracking catalyst powder into alumina powder, granulating, drying and roasting to obtain SiO2Content of 3.5%, WO3The carrier contains 1.6 percent of NiO and 0.4 percent of NiO (both are analyzed as a standard after being roasted at 470 ℃). The carrier was soaked in nickel acetate aqueous solution at equal volume to newly increase NiO content to 2.7% (using 470 ℃ roasting analysis as standard), and then dried at 180 ℃ for 3 hours to obtain a first-stage semi-finished product F1. And then vulcanizing the F1 by adopting dry vulcanization to convert the metal in the F1 into a corresponding metal sulfide, and vulcanizing the F2 by using hydrogen with the hydrogen sulfide content of 2 percent for 5 hours at 330 ℃ under the condition of 4.2 MPa. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium metatungstate and nickel acetate to perform equal-volume impregnation on F2, so that the later is added with WO37.0% (using 470 ℃ roasting analysis as standard) and NiO 0.9% (using 470 ℃ roasting analysis as standard), drying at 85 deg.C for 5 hr under nitrogen atmosphere, and roasting at 340 deg.C for 3 hr to obtain WS2-Ni2S3-WO3-NiO/Al2O3-SiO2Catalyst G3.
Comparative example 1
This comparative example is compared to example 2.
Soaking ammonium molybdate and nickel nitrate aqueous solution on an alumina carrier in equal volume to ensure that MoO is coated on a section of semi-finished product3The content of the NiO is 7.0 percent and the NiO content is 2.0 percent (both are based on the analysis after roasting at 470 ℃ as the standard), and then the MoO is obtained after drying for 4 hours at 150 ℃ and roasting for 3 hours at 340 DEG3-NiO/Al2O3And (4) catalyst DB.
Comparative example 2
This comparative example is compared to example 5.
In SiO2Soaking 7.3% silicon-containing alumina carrier with ammonium metatungstate and nickel acetate aqueous solution in equal volume to obtain a semi-finished product313.0 percent of NiO content and 12.0 percent of NiO content (both taking the analysis after roasting at 470 ℃ as a standard), then drying for 3 hours at 160 ℃, roasting for 3 hours at 340 ℃ to obtain WO3-NiO/Al2O3-SiO2Catalyst DE.
Example 8
This example illustrates the reactivity of the silicon capture agent provided by the present invention to coker naphtha. Representing the influence degree of the active components on the pore volume and the specific surface area of the silicon catching agent through the specific surface area loss rate of the silicon catching agent immediately after vulcanization; the hydrogenation performance of the active component is measured by the carbon deposition amount on the silicon capturing agent after operation; the desiliconization and silicon capturing performance of the silicon capturing agent is measured by the content of saturated silicon on the silicon capturing agent after operation.
The evaluation feedstock used was coker naphtha supplied from a refinery in medium petrochemicals.
Catalysts A3 to G3, comparative examples DB and DE were each evaluated for reaction performance using a 200mL trickle bed hydrogenation unit.
Presulfurizing conditions of the catalyst: using a catalyst containing 2.1wt% CS2The space velocity of the aviation kerosene is 1.0h-1Presulfurizing the catalyst at the pressure of 3.5MPa with the hydrogen-oil volume ratio of 360: 1.
The prevulcanisation process is as follows: feeding pre-vulcanized oil at 100 ℃, feeding oil for 1h, vulcanizing at constant temperature for 2h, heating to 130 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 240 ℃ at 6 ℃/h, vulcanizing at constant temperature for 3h, heating to 260 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 330 ℃ at 12 ℃/h, vulcanizing at constant temperature for 16h, naturally cooling to 110 ℃, and finishing the pre-vulcanization.
The evaluation reaction conditions were: the operating pressure is 3.4MPa, the reaction temperature is 260 ℃, and the volume space velocity is 1.6h-1The hydrogen-oil volume ratio was 370:1, and the evaluation results are shown in Table 1.
TABLE 1 Properties of catalyst and evaluation results
The above evaluation results show that the active metal of the silicon capturing agent has higher sulfidation degree, the loss of the specific surface area of the catalyst after the completion of the sulfidation is low, the carbon deposition amount is low after the operation is finished, and the saturated silicon capacity is high.
Claims (14)
1. An oil silicon capturing agent comprises a carrier and a hydrogenation active component, and is characterized in that: the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide, wherein the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni; based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.1-12.2 wt%, the VIB group metal oxide accounts for 0.5-17.2 wt%, the VIII group metal oxide accounts for 0.1-9.0 wt%, and the carrier accounts for 61.6-99.3%.
2. The oil silicon capture agent of claim 1, wherein: based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.4-6.8 wt%; 1.6-9.3 wt% of VIB group metal oxide, 0.2-2.0 wt% of VIII group metal oxide and 81.9-97.8% of carrier.
3. The oil silicon capture agent of claim 1, wherein: the carrier is porous inorganic refractory oxide, and is selected from one or more of oxides of elements in II group, III group, IV group and IVB group of the periodic table.
4. The oil silicon capture agent of claim 1, wherein: the carrier is one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide, aluminum magnesium oxide, a hydrocracking catalyst containing silicon oxide or a hydrocracking catalyst containing a molecular sieve.
5. A method for preparing the oil silicon catching agent as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps: (1) dipping the silicon catching agent carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material; (2) by containing groups VIB and
and (3) dipping the vulcanized material obtained in the step (1) in a dipping solution of the group metal, and then drying and roasting the dipped material in an inert atmosphere to obtain the oil silicon catching agent.
6. The method of claim 5, wherein: the second step of (1)
The group metals are Ni and/or Co.
7. The method of claim 5, wherein: the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.
8. The method of claim 5, wherein: the vulcanization treatment in the step (1) adopts dry vulcanization or wet vulcanization; wherein the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide.
9. The method of claim 5, wherein: the vulcanization treatment conditions in the step (1) are as follows: the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 hours.
10. The method of claim 5, wherein: the VIB group metal in the step (2) is Mo and/or W; the first mentioned
The group metals are Ni and/or Co.
11. The method of claim 5, wherein: the inert atmosphere in the step (2) 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.
12. The oil silicon capturing agent of any one of claims 1 to 4 is applied to coking dry gas hydrogenation, coking naphtha hydrogenation, reforming prehydrogenation and coking diesel oil hydrogenation processes.
13. Use according to claim 12, characterized in that: before the application of the oil silicon capturing agent, the oil silicon capturing agent needs to be subjected to vulcanization treatment, wherein the vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more 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 hours.
14. Use according to claim 13, characterized in that: after the oil product silicon capturing agent is vulcanized, XPS energy spectrum analysis is adopted, wherein the molar proportion of the VIB group metal content of +4 valence state in the total VIB group metal content is 70-100%.
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