CN106378174A - A hydrofining catalyst - Google Patents
A hydrofining catalyst Download PDFInfo
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- CN106378174A CN106378174A CN201610683670.7A CN201610683670A CN106378174A CN 106378174 A CN106378174 A CN 106378174A CN 201610683670 A CN201610683670 A CN 201610683670A CN 106378174 A CN106378174 A CN 106378174A
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- catalyst
- mcm
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- present
- gasoline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- -1 dimolybdenum nitride Chemical class 0.000 claims abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910003178 Mo2C Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000009432 framing Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 abstract description 40
- 239000011593 sulfur Substances 0.000 abstract description 40
- 239000003502 gasoline Substances 0.000 abstract description 39
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 28
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 238000011160 research Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 235000016768 molybdenum Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 230000002079 cooperative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- B01J35/19—
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2300/70—Catalyst aspects
Abstract
A hydrodesulfurization catalyst is disclosed. The catalyst comprises a carrier and an active component. The carrier is MCM-41 the synthesis skeleton of which is doped with Co<2+> that is a heteroatom, with the doping amount being 0.56-0.75% by weight of the MCM-41. The active component is a mixture of dimolybdenum nitride (Mo<2>N), tungsten nitride (W2N), molybdenum carbide (Mo<2>C) and tungsten carbide (WC). The total weight of the active component is 1-15% of the weight of the carrier MCM-41. The catalyst also comprises a catalytic promoter that is a mixture of TiO2, CeO2, V2O5 and NbOPO4. The catalyst can reduce the total sulfur content of FCC gasoline to 10 ppm or below, thus meeting the national V emission standard of gasoline in China. In addition, through adoption of the catalyst, the octane number of the FCC gasoline is not obviously reduced.
Description
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of hydrodesulfurization catalyst for refining, is more preferably related to one
Plant FCC gasoline hydrodesulfurization and reduce the catalyst that octane number reduces amplitude.
Background technology
Enter 21st century, the demand of fuel oil and use increase substantially, and sulfur-containing compound therein is brought
Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil produces through engine combustion
(SOx) it is discharged in the air, produce acid rain and the pollution of fumes of sulphuric acid type etc., cause atmospheric pollution.
Sulfur is that nature is present in one of gasoline harmful substance, and in gasoline product, more than 80% sulfur carrys out self-catalysis and splits
Change (FCC) gasoline, with the continuous change weight of crude oil, the sulfur content in FCC gasoline also can be continuously increased.External gasoline is generally from
FCC (34%), catalytic reforming (33%), and alkylation, the technique such as isomerization and etherificate (about totally 33%)；And home-produced fuel
80% is from FCC gasoline.Sulfur due in gasoline 85%～95% is derived from FCC gasoline so that sulfur content in China's gasoline
A lot of more than external gasoline.A lot of experts have carried out the research that sulfur affects on motor vehicle exhaust emission, and result shows：If by gasoline
In sulfur content from 450 μ g g-1It is reduced to 50 μ g g-1, NO in vehicle exhaustxAverage 9%, the CO that reduces averagely reduces
19%, HC averagely reduce 18%, and Toxic averagely reduces 16%.Thus, effective fuel oil hydrodesulfurization technology, to society, warp
Ji, the development of environment play the role of important.
Most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as at present, especially selective hydrogenation
Desulfurization technology, the saturation of suppression alkene of trying one's best while removing gasoline a large amount of sulfur-containing compound is to reduce loss of octane number.
This kind of technology has operating condition and relaxes, and yield of gasoline is high, and hydrogen consumes the features such as low and loss of octane number is little.Hydrodesulfurization technology
Key is the selection of Hydrobon catalyst, and the cobaltmolybdate catalyst of support type is the important gasoline hydrodesulfurizationcatalyst catalyst of a class,
Typically cobalt molybdenum is loaded on porous support (as aluminium oxide, silicon oxide, activated carbon or its complex carrier), be widely used in adding
In hydrogen sweetening process, to obtain premium-type gasoline product.
Hydrodesulfurization (HDS) technology is to grow up the fifties, and the nineties, this technology welcome second improving and developing
Individual peak period, its technical maturity, all the time, become sulfur, nitrogen, oxygen in removing distillate, improve oil product Practical Performance and clear
The maximally efficient means of cleanliness.The activity and selectivity of catalyst is the key factor of impact hydrofinishing efficiency and depth,
The economy that high performance catalyst is brought and environmental benefit are very significant, have therefore attracted numerous enterprises and researcher to put into
To in efficient catalyst exploitation, the catalyst prod that develop many function admirables, differs from one another.Hydrogenation technique is sent out rapidly
The basic reason of exhibition is the development of catalyst, but can cause alkene saturation and product octane number while routine techniquess desulfurization
(RON) decline, therefore can desulfurization and the few selective hydrogenation new technique of loss of octane number to become HDS method in recent years improved
Main way.
The RESOLVE technological development catalytic cracking of Akzo Nobel company exploitation reduces the RESOLVE of content of sulfur in gasoline
Additive product series, using high hydrogen transfer activity component and ADM-20, can make cracking gasoline sulfur content reduce by 20%,
RESOLVE-700 gasoline reduction sulfur additives are currently in industrial evaluation.
Containing Sulfur in Exxon research engineering company and Akzo Nobel company joint development selectively removing FCC gasoline
The Scanfining technology of compound, and in 1998, this technology is pushed to industrialization.It adopts traditional hydrotreating flow process, leads to
Cross meticulous selecting catalyst (RT-225), make loss of octane number and hydrogen consumption reach minimum.
The Prime-G technology of French IFP exploitation, this technology is developed by French studying and designing institute (IFP), using dual catalyst
System.Its process conditions relaxes, and hydrogenation of olefins activity is low, alkene saturation and cracking reaction does not occur, liquid yield reaches 100%,
Desulfurization degree is more than 95%, and loss of octane number is few, and hydrogen consumption is low.By FCC heavy petrol hydrodesulfurization, being in harmonious proportion the gasoline product obtaining can
To realize the target of sulfur content 100～150 μ g g-1；By the hydrodesulfurization respectively of FCC petroleum benzin, achievable sulfur content 30 μ
The target of g g-1.
For the feature of domestic FCC gasoline sulfur-bearing, Fushun Petrochemical Research Institute (FRIPP) develops FCC gasoline and selects
Property hydrogen addition technology (OCT-M) and full distillation gasoline selective hydrogenation technology (FRS), device can produce sulfur nutrient and be not more than
150μg·g-1GB III gasoline.OCT-M technology, after Shijiazhuang Oil Refinery, China Petrochemical Corp. continuously runs 17 months, adopts
Two kinds of prioritization schemes that FRIPP recommends, after FCC gasoline hydrogenation, sulfur nutrient reaches GB III and IV standard.
On May 5th, 2016, department of the Committee of Development and Reform, the Ministry of Finance, Chinese Ministry of Environmental Protection etc. seven issues with regard to printing and distributing《Accelerate finished product oil quality
Upgrade job scheme》Notify, scheme clearly expands automobile-used vapour, diesel oil state five standard execution scope.From original Jing-jin-ji region, length three
Angle, Pearl River Delta region key cities expand whole eastern region 11 provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, rivers to
Soviet Union, Zhejiang, Fujian, Shandong, Guangdong and Hainan).Before 31 days October in 2015, eastern region is protected possesses manufacturing country five mark for enterprise
Quasi- motor petrol (oil of blend component containing ethanol petrol), the ability of derv fuel.From 1 day January in 2016, eastern region supplies comprehensively
Motor petrol (ethanol petrol containing E10), the derv fuel (biodiesel containing B5) of state five standard should be met.
At present, the main method reducing FCC gasoline sulfur content is catalytic desulfurhydrogenation.But hydrotreating method exists such as
Lower deficiency：(1) equipment investment is big；(2) it is hydrogenated with the severe reaction conditions of de- thiophenic sulfur, operating cost is high；(3) alkene is de- in hydrogenation
Easily there is saturation under the conditions of sulfur, not only consume a large amount of hydrogen, and lead to octane number to reduce.FCC gasoline desulfurization degree requires
Higher, operating condition is harsher, and the loss of octane number is also bigger.
How a kind of Hydrobon catalyst is therefore provided, can effectively the sulfur content in gasoline be controlled in below 10ppm,
To meet state five standard, octane number loss simultaneously is less or does not lose, and is the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing a kind of Hydrobon catalyst, this catalyst can be by the total sulfur in FCC gasoline
Content is reduced to below 10ppm, to meet gasoline state five standard.Meanwhile, this catalyst using the octane also making FCC gasoline
Value significantly reduces.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of catalyst of hydrodesulfurization, described catalyst includes carrier and active component.
Described carrier is to mix hetero atom Co in synthesis framing structure2+MCM-41.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst also contains catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing
Thing；
MCM-41 is ordered into mesoporous material, and its duct is in six side's ordered arrangement, uniform in size, and aperture size can be with during synthesis
Directed agents and the difference of synthetic parts is added to change between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g,
MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), be conducive to organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49,
MCM56, carries out contrast test selection, finds the goal of the invention only having MCM-41 can reach the present invention, other mesoporous materials are all
There is such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, the therefore present invention selects to use
MCM-41 is as carrier basis.
Silica MCM-41 acidity itself is very weak, is directly used as catalyst activity relatively low.Therefore, the present invention changes to it
Property, to increase its catalysis activity.The present invention approach modified to MCM-41 mesopore molecular sieve be：In MCM-41 building-up process,
Add Co2+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part skeleton unit
Element is thus in the skeleton of embedded molecular sieve, improve catalysis activity, absorption and the heat of MCM-41 mesopore molecular sieve on the whole
Mechanical stability can wait.
Although the method that MCM-41 mesopore molecular sieve is modified or approach are a lot, inventor finds, the present invention urges
Agent can only be using doping Co2+MCM-41 just enable sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted doping in MCM-41:Al3+、Fe3+、Zn2+、Ga3+In the ion producing anionic surface center, find all can not
Realize described effect.Modification approach another with inventor passes through ion exchange by Cu2+It is supported on MCM-41 inner surfaces of pores to compare,
The isomorphous substitution approach of the present invention is more stable.Although described mechanism is not known at present, this has no effect on the reality of the present invention
Apply, according to well-known theory and it is experimentally confirmed that it has cooperative effect and the active component of the present invention between to inventor.
Described Co2+Must control within specific content range in the doping in MCM-41, its doping is with weight
Meter, be the 0.56%-0.75% of MCM-41 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%th, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can lead to drastically reducing of octane number.More pleasurable, when
Co2+When the doping in MCM-41 controls in the range of 0.63%-0.72%, it is the strongest to the control of octane number, works as drafting
With Co2+When doping is transverse axis, curve chart with target octane number as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, the desulfurized effect that it produces, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is 1%-15%, the preferably 3-12% of carrier MCM-41 weight, further preferably
5-10%.For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%th, 14%, 14.5% etc..
In the present invention, being particularly limited to active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor finds, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6):(0.28-
0.45):(0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
Should in the range of, can realize that in FCC gasoline, sulfur content controls in below 10ppm and octane number is not decreased obviously.?
That is, four kinds of active components of the present invention are 1 only in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2) when,
Just possesses cooperative effect.Outside this molar ratio range, or omit or replace any one component, do not enable to assist
Same effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5):(0.35-0.45):(0.8-1.0), more preferably 1:(0.45-0.48):(0.4-0.45):(0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The third object of the present invention is to provide the promoter of described catalyst.Catalyst of the present invention also contains
Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, there is a catalyst aid of maturation, such as P, F and B etc., its
For adjusting the property of carrier, weaken strong interaction between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent in application with the carrier of the present invention with active component when, for high sulphur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounds,
Find eventually to adopt TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improving its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no the ratio of fixation that is to say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention adopts2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although not having specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching
To the requirement of effective dose, the content of catalyst aid effect, the 1-7% of such as carrier quality can be played.The present invention is selecting
During find, omitting or replacing one or more of described auxiliary agent, the technique effect all not reaching the present invention (improves water
Heat stability, reduces coking and improves service life) close that is to say, that there is specific cooperation between the catalyst aid of the present invention
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop rise is relatively
Hurry up.The present invention also once attempted introducing other phosphate, although this attempt introducing phosphate anion, but equally existed hydro-thermal
Stability is relatively slightly worse, and its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduces catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Do not introduce the catalyst aid particularly niobium phosphate of the present invention,, compared to the scheme introducing catalyst aid, its defect is only phase for it
To.I.e. this defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention,
Institute mentioned by the present invention is advantageous or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, it is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods of routine, people in the art
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
The catalyst of the present invention, can be used for the hydrodesulfurization of gasoline, is particularly suitable for the hydrodesulfurization of FCC gasoline.
The present invention passes through to choose specific incorporation hetero atom Co2+MCM-41 as carrier, and the nitrogen choosing special ratios
Change two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2, as active component, described catalyst also contains catalysis to be helped for C and tungsten carbide wc
Agent, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, to FCC
The hydrodesulfurization of gasoline can control total sulfur content be less than 5ppm, simultaneously octane number reduce amplitude control within 0.5-2%.
Specific embodiment
The present invention is illustrated to the catalyst of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping Co2+MCM-41, doping in MCM-41 for the Co2+
Control the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content be carrier quality 10%, its mol ratio be 1:0.4:0.3:0.8.
Described Catalyst packing is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Become, reaction bed temperature is measured with UGU808 type temp controlled meter, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory
Plug micro pump continuous conveying, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC D07-11A/ZM gas mass flow gauge control
Flow velocity processed, loaded catalyst is 2kg.Reacted product carries out gas-liquid separation after the cooling of water-bath room temperature.
Raw materials used for full fraction FCC gasoline, it contains alkene 25.3m%, aromatic hydrocarbons 40.2m%, alkane 28.8m%, grinds
Studying carefully method octane number is 94.2, total sulfur content 660 μ g/g.
Control reaction condition be：370 DEG C of temperature, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 3h-1.
Test final product, its research octane number (RON) still reaches 94.0, and total sulfur content is reduced to 2ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is the MCM-41 of doping Co2+, doping in MCM-41 for the Co2+
Amount controls the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide
The total content of WC is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45):1.2.
Remaining condition is same as Example 1.
Test final product, its research octane number (RON) still reaches 93.9, and total sulfur content is reduced to 2ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Test final product, its research octane number (RON) is 81, total sulfur content is 22ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, remaining condition is constant.
Test final product, its research octane number (RON) is 82, total sulfur content is 16ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Test final product, its research octane number (RON) is 82, total sulfur content is 21ppm.
Comparative example 4
Doping in MCM-41 for the Co2+ in embodiment 1 is controlled the 0.5% of carrier quality, remaining condition is not
Become.
Test final product, its research octane number (RON) is 89, total sulfur content is 9ppm.
Comparative example 5
By the Co in embodiment 12+Doping in MCM-41 controls the 0.8% of carrier quality, and remaining condition is constant.
Test final product, its research octane number (RON) is 87, total sulfur content is 12ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+When doping is different, all reach
Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other
Possess cooperative effect between component, create unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Test final product, its research octane number (RON) is 84, total sulfur content is 25ppm.
Comparative example 7
Omit the WC in embodiment 1, remaining condition is constant.
Test final product, its research octane number (RON) is 83, total sulfur content is 24ppm.
, between several active component of catalyst of the present invention, there is specific connection in above-described embodiment and the explanation of comparative example 6-7
System, being omitted or substituted one of which or several, all can not reaching the certain effects of the application it was demonstrated which creating cooperative effect.
Embodiment 3
Catalyst aid TiO is contained in catalyst2、CeO2、V2O5And NbOPO4, its content respectively 1%, 1.5%, 1% and
3%, remaining is same as Example 1.
Test final product, after it uses 3 months, beds pressure drop is not any change, use compared to same
The beds pressure drop of time embodiment 1 reduces 18%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 5%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 4%.
Embodiment 3 and comparative example 8-9 show, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
One of or several groups of timesharing, all can not reach the present invention and add minimizing coking during catalyst aid thus stoping catalyst bed
The high technique effect of lamination falling-rising.That is, it demonstrates the service life that the catalyst aid of the present invention can improve described catalyst,
And other catalyst aid effects are not so good as this specific catalyst aid.
Applicant states, the present invention illustrates the catalyst of the present invention by above-described embodiment, but the present invention does not limit to
In above-mentioned catalyst, that is, do not mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.The skill of art
Art personnel are it will be clearly understood that the adding of any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element
Plus, the selection of concrete mode etc., all fall within protection scope of the present invention and open within the scope of.
Claims (6)
1. the de- refined agent of a kind of hydrogenation, described catalyst include carrier and active component it is characterised in that
Described carrier is to mix hetero atom Co in synthesis framing structure2+MCM-41, its doping is MCM-41 weight
0.56%-0.75%；
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described activity
The total content of component is the 1%-15% of carrier MCM-41 weight；
Described catalyst also contains catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.
2. Hydrobon catalyst as claimed in claim 1 is it is characterised in that hetero atom Co2+Doping be MCM-41 weight
The 0.63%-0.72% of amount.
3. Hydrobon catalyst as claimed in claim 1 is it is characterised in that the total content of described active component is carrier
The 3-12% of MCM-41 weight, preferably 5-10%.
4. Hydrobon catalyst as claimed in claim 1 is it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5):(0.35-0.45):(0.8-1.0), more preferably 1:
(0.45-0.48):(0.4-0.45):(0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. Hydrobon catalyst as claimed in claim 1 is it is characterised in that described Hydrobon catalyst is used for FCC vapour
The hydrodesulfurization of oil refines.
6. Hydrobon catalyst as claimed in claim 1 is it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective contain
Amount is respectively the 1-7%, preferably 2-4% of carrier quality.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 张文成等: "改性MCM-41分子筛的制备及加氢催化性能研究", 《第十一届全国青年催化会议论文集（下）》 * |
| 阙国和: "《石油组成与转化化学》", 31 December 2008, 中国石油大学出版社 * |
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