CN1218021C - Gasoline hydrogenation catalyst, its prep. and application in lowering olefin by desulfurization - Google Patents
Gasoline hydrogenation catalyst, its prep. and application in lowering olefin by desulfurization Download PDFInfo
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- CN1218021C CN1218021C CN 02116267 CN02116267A CN1218021C CN 1218021 C CN1218021 C CN 1218021C CN 02116267 CN02116267 CN 02116267 CN 02116267 A CN02116267 A CN 02116267A CN 1218021 C CN1218021 C CN 1218021C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 title description 15
- 230000023556 desulfurization Effects 0.000 title description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000000969 carrier Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 8
- 150000004706 metal oxides Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 238000004073 vulcanization Methods 0.000 abstract 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000004523 catalytic cracking Methods 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003292 glue Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229910017313 Mo—Co Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 241000219793 Trifolium Species 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance 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
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 olefin hydrocarbon Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The present invention relates to a gasoline hydrogenation catalyst, a preparation method thereof and the application thereof in vulcanization and olefin reduction. The catalyst comprises the components with the weight percentage: 20 to 90w% of carriers with TiO2 components, 0.1 to 8w% of a VIII-group metal oxide as an active component A, 1 to 13w% of a VIB-group metal oxide as an active component B and a binding agent as the rest. FCC gasoline containing sulfur and olefin is processed by the catalyst after prevulcanization under the condition of slow hydrogenation, and the catalyst has high hydrogenation vulcanization activity and high selectivity. Compared with the traditional hydrogenation catalyst, the catalyst causes low loss of the octane number of the gasoline under the condition of an identical hydrogenation vulcanization level, and the liquid yield of products is high and reaches 99w%.
Description
Technical field
The present invention relates to the gasoline that contains sulphur, alkene is carried out the used Catalysts and its preparation method of technological process of hydrotreatment.Be particularly related to a kind of gasoline hydrogenation catalyst and method for making and its application in desulfurating and reducing olefinic hydrocarbon.
Background technology
Traditional hydrogenating desulfurization, alkene is saturated and denitrification catalyst usually with porous alumina or contain a small amount of SiO
2Or B
2O
3Aluminum oxide be carrier, be active ingredient with VIII family and group vib metallic element.Another kind of hydrogenating desulfurization, alkene is saturated and denitrification catalyst is based on the dual-function catalyst of molecular sieve.
FCC (catalytic cracking) gasoline can be handled the organosulfur reduce wherein and the content of alkene by selective hydrogenation, thereby reaches environmental requirement.But the octane number barrel rate of loss of handling back gasoline changes to some extent along with the performance difference of the hydrogenation degree of depth and catalyzer.For example US 6,042, and 719 have reported with traditional Co-Mo/Al
2O
3Catalyzer or Co-Mo/ZSM-5 dual-function catalyst carry out the method for deep desulfuration at low temperatures to FCC gasoline.The gasoline that this method is produced when sulphur content reduces, the loss of the motor-method octane number of gasoline less than 5%, research octane number (RON) loses less than 10%.US 5,865, and 988 adopt gasoline secondary hydrogenation quality upgrading technology, and the catalyzer of first segment process is the molecular screen material with ZSM-5 of central hole structure.This catalyzer has enough acidity, can satisfy the needs of cracking, aromizing and alkylated reaction.The condition that this catalyzer is used makes normal paraffin might be isomerizated into the higher branched paraffin of octane value, and the cyclization of olefines that can control in the raw material is aromatic hydrocarbons, the alkylation degree of aromatic hydrocarbons and alkene.The catalyzer of second segment process is traditional Co-Mo/Al
2O
3Or Ni-Mo/Al
2O
3The catalyst hydrogenation desulfurization.The content of sulfur in gasoline that this method is produced is removed to＜and during 50ppm, Study of Gasoline method octane value is reduced to 90.3 by 93, and it is 92.1% that liquid is received.US3,759,821 have disclosed a kind of FCC quality of gasoline upgrading process, and gasoline distillation is become the weight cut, and with the last running of ZSM-5 catalyst treatment, processed then cut is blended back light constituent.US5,143,596 and EP 420,326 B1 described and utilize sulfur-tolerant type to select the quality upgrading technology of aromatized catalyst the sulfur-bearing stock oil in the gasoline-range, this catalyzer is the crystalline silicate that contains metal, comprising as containing the ZSM-5 zeolite of gallium, under severe condition, typical temperature is 400 ℃ at least, usually higher, as 500 ℃, have at least 50% alkane to become aromatic hydrocarbons, and that liquid is received is more much higher than reforming with conversion of olefines.
In above-mentioned disclosed patent documentation report, regardless of mechanism, its common shortcoming is that desulfurating and reducing olefinic hydrocarbon all can cause the processed oil octane value to descend in the hydrogenation process.This has produced contradiction with the demand that at present processed oil is cleaned in high-octane rating, low pollution.It is nearly 80% that particularly China FCC gasoline accounts for gasoline component, and olefin(e) centent is up to 45～65% in the FCC gasoline, and this substantial contradiction seems more outstanding under new environmental protection standard.In addition, above-mentioned patent US5,865,988, US5,346,609, US5,143,696 and EP420, the described technology of 326 B1 also exists total liquid to receive (C5
+) lower problem, generally have only about 90w%.Therefore, how to create a kind ofly in existing desulfurization preferably with fall the alkene ability, can make in desulfurization again and fall that liquid in the olefin hydrocarbon is received and the catalyzer of loss of octane number minimum, expect the problem that solves always with regard to becoming this area.
In addition, US 4,313, and 817 disclose the catalyzer of a kind of VGO of being used for (normal decompression oil) hydrocracking, and its purpose is production high value lube stock and oil fuel.The effect of its catalyzer is the pour point that can significantly reduce lube stock.In addition, US4,443,329 disclose hydrogenating desulfurization, the denitrification catalyst of raw materials such as a kind of VGO.Its purpose also is the pour point that is to reduce product.
Above-mentioned two pieces of patent documentations, disclosed content or to be used for VGO be the hydrocracking of raw material or to be used for VGO be hydrogenating desulfurization, the denitrogenation of raw material.They all do not provide and enlighten with FCC (catalytic cracking) gasoline is that raw material, purpose are that the catalyzer of alkene and the content of method for making fall in hydrogenating desulfurization.
Summary of the invention
The objective of the invention is to improve on the basis of existing technology, prepare a kind of hydrogenating desulfurization and olefine lowering catalyst that is applicable to that the upgrading of FCC quality of gasoline requires.
Gasoline hydrogenation catalyst of the present invention is achieved in that
Catalyzer of the present invention is by the weight percent meter to catalyzer, and its component comprises:
Contain the TiO that consumption is 40～80w%
2And TiO
2-ZrO
2Perhaps TiO
2And TiO
2-SiO
2And surplus is the carrier of binding agent;
The A active ingredient: the content of VIII family metal oxide is 0.1～8w%;
The B active ingredient: the content of group vib metal oxide is 1～13w%.
In the concrete process of implementing:
In the above-mentioned catalyzer, the preferred CoO of VIII family metal oxide, NiO.
In the above-mentioned catalyzer, the preferred MoO of group vib metal oxide
3, WO
3
Wherein the preferred content of VIII family metal oxide is 1～5w%.
The preferred content 3～8w% of group vib metal oxide wherein.
Described carrier comprises that consumption is the TiO of the preferred 6w% of 40～80w%
2, TiO
2-ZrO
2, TiO
2-SiO
2In one or more oxide compounds, surplus is Al
2O
3, SiO
2Binding agent.Described TiO
2-ZrO
2And TiO
2-SiO
2In the oxide compound, TiO
2: ZrO
2And TiO
2: SiO
2Weight ratio be 3: 1.Described binding agent is preferably at least a in aluminum oxide dry glue powder, silicon sol, the aluminium colloidal sol.
The present invention's two is above-mentioned Preparation of catalysts methods, the steps include:
(1) preparing carriers: will comprise TiO according to described proportioning
2Pinch through mixing with the carrier component of binding agent, make after the moulding, drying, roasting;
(2) dipping active ingredient: use the excessive dipping of at least two kinds of solution that is selected from the solution that comprises A active ingredient and B active ingredient by 1) the gained carrier makes catalyzer after drying, the roasting again.
In the concrete process of implementing:
(1) takes by weighing TiO
2, TiO
2-ZrO
2, TiO
2-SiO
2Wherein the powder of one or more oxide compounds (the unified down titanium valve that is called) adds and contains Al
2O
3And/or SiO
2Binding agent mixes and pinched 10～40 minutes; Preferably 15～25 minutes.
(2) by (1) gained material extruded moulding on banded extruder;
(3) by (2) gained material, under 60～140 ℃ of temperature, dry 1～5 hour; Preferably 100～120 ℃ were descended dry 3～4 hours.
(4) by (3) gained material, under 300～500 ℃ of temperature, roasting 2～5 hours; Preferably under 400～500 ℃, roasting 2～5 hours.
(5) with containing the excessive dipping of solution of molybdenum (or tungsten) and nickel and/or cobalt by (4) gained carrier; Solution is to be selected from a kind of in Mo-Ni, Mo-Ni-Co, Mo-Co, the W-Ni solution
(6) by (5) gained material, under 60～140 ℃ of temperature, dry 1～5 hour; Preferably under 100～120 ℃, dry 3～4 hours.
(7) by (6) gained material, under 350～500 ℃ of temperature, roasting 1～4 hour.Preferably under 400～500 ℃, roasting 2～5 hours.
Can add an amount of expanding agent in step (1), described expanding agent can be the blue or green powder in field, starch, polyvinyl alcohol, methylcellulose gum, the blue or green powder in field preferably, and its add-on can be 2～10w% of mixed powder, preferably 4～6%; Aluminum oxide dry glue powder can be selected the thin aluminium stone of the plan of macropore, large specific surface.
The described extruded moulding process of step in the step (2), the extrusion orifice plate can be selected as required, and support shapes is generally cylindrical or the cross section is the strip of three (four) leaves grass shape, and diameter or equivalent diameter are 1～2mm.
The described solution of step (5) is Mo-Ni or Mo-Ni-Co or Mo-Co or W-Ni solution, and the concentration of solution is determined by the water-intake rate of carrier and the metal component content of final catalyzer.
Catalyzer of the present invention is formed, and in catalyst weight, is MoO
3Or WO
31～13w%, preferably 3～8w%; CoO and/or NiO0.1～8.0w%, best 1.0～5.0w%.
With TiO
2Be carrier, the gasoline hydrogenation of the present invention that supports Mo (or W), Ni or Co preparation is handled catalyzer, and its pore volume is 0.2～0.5ml/g, and specific surface is 120～250m
2/ g.
The present invention's three is above-mentioned catalyzer application in desulfurizing and reducing olefine for gasoline.Its processing condition are: reaction pressure 0.1～3Mpa, preferred 1～2Mpa; 180～380 ℃ of temperature of reaction, preferred 220～350 ℃; Liquid air speed 2～8h
-1, preferred 3～6h
-1
Gasoline hydrodesulfurizationmethod olefine lowering catalyst of the present invention is with TiO
2Be the dual-function catalyst of carrier, one of its function is to utilize TiO
2Improve the hydrogenation activity of catalyzer with the strong interaction of reactive metal, thereby reach the purpose that reduces temperature of reaction, because low-temp reaction helps the process of hydrocarbon isomerization; Two of its function is to utilize the acidity of carrier itself to improve reactions such as hydrocarbon isomerization, aromizing simultaneously.When organosulfur hydrocracking and hydrogenation of olefins were saturated, the loss of octane number of gasoline was littler than other hydrogenation catalyst like this.And use the gasoline octane rating rate of loss of traditional catalyst to be greater than catalyzer of the present invention.And it is also much higher than catalyzer of the present invention based on the temperature of reaction that molecular sieve catalyst is required.
As everyone knows, the pore structure of load hydrogenation processing catalyzer is determined by the pore structure of its carrier basically.The present invention at first selects proper raw material for the carrier of extruded moulding, and promptly raw material will have concentrated pore distribution, macropore, large specific surface TiO that Deqing branch office of real Beijing Haishunde Titanium Catalyst Co., Ltd. used herein produces
2, TiO
2-ZrO
2, TiO
2-SiO
2Dry glue powder; Next be mix pinch or roasting process in carry out suitable processing, have proper pore structure to guarantee carrier.Add expanding agents such as adding carbon black, starch, flour, the blue or green powder in field, macromolecule organic, tensio-active agent in expanding agent such as the raw material powder in this external carrier moulding process and further improve the carrier hole structure.Because the alkene in the gasoline is aggregated in the catalyst surface coking easily, and the catalyzer that is prepared as of above-mentioned carrier is fit to the FCC gasoline hydrodesulfurizationmethod and falls alkene rational pore structure is provided, and this helps catalyzer and improve the anti-coking performance in the desulfurating and reducing olefinic hydrocarbon process.Catalyzer of the present invention under than the demulcent hydroconversion condition, is handled the FCC gasoline of sulfur-bearing, alkene after prevulcanized, show very high hydrodesulfurization activity and selectivity.Promptly compare with traditional hydrogenation catalyst, under the horizontal situation of identical hydrogenating desulfurization, the loss of octane number that shows gasoline is smaller, and the liquid of product is received than higher, reaches 99w%.
Embodiment
The technical characterictic that the invention is further illustrated by the following examples.
Embodiment 1
The titanium dioxide dry glue powder that Deqing branch office of Beijing Haishunde Titanium Catalyst Co., Ltd. is produced (contains TiO
280%) 200g adds the blue or green powder 10g in field, mixes.Alumina gel: silicon sol (1: 1) 120g adds in the aforesaid material, fully mix pinch after, on preceding crowded formula twin screw banded extruder, be extruded into the trifolium shape bar that equivalent diameter is 1.4mm, the gained bar that wets is dry 2 hours of 60 degree, dry 2 hours of 120 degree, 500 degree roastings 3 hours, get carrier A, its character sees Table 1, through the Mo-Co solution impregnation, through 110 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyst A 1, its character sees Table 2.
Embodiment 2
The titanium dioxide dry glue powder that Deqing branch office of Beijing Haishunde Titanium Catalyst Co., Ltd. is produced (contains TiO
280%) 100g and titanium-zirconium dry glue powder (contains ZrO
225%) 100g adds the blue or green powder 10g in field, mixes.1: 1 alumina gel and silicon sol 120g are added in the aforesaid material, on preceding crowded formula twin screw banded extruder, be extruded into the trifolium shape bar that equivalent diameter is 1.4mm after fully mixed the pinching, the gained bar that wets, dry 2 hours 120 ℃ of dryings of 60 degree 2 hours, 500 ℃ of roastings 3 hours, get carrier B, its character sees Table 1.Through the Mo-Co solution impregnation, through dry 5 hours of 110 degree, 450 ℃ of roastings 2 hours, catalyst B 1, its character sees Table 2.
Embodiment 3
The titanium dioxide dry glue powder that Deqing branch office of Beijing Haishunde Titanium Catalyst Co., Ltd. is produced (contains TiO
280%) 100g and titanium-silicon dry glue powder (contains SiO
225%) 100g adds the blue or green powder 10g in field, mixes.Alumina gel 120g is added in the aforesaid material, after fully mixed the pinching, on preceding crowded formula twin screw banded extruder, be extruded into the trifolium shape bar that equivalent diameter is 1.4mm, the gained bar that wets is 60 ℃ of dryings 2 hours, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 3 hours, get support C, its character sees Table 1, through the Mo-Co solution impregnation, through 110 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyzer C1, its character sees Table 2.
Embodiment 4
The titanium dioxide dry glue powder that Deqing branch office of Beijing Haishunde Titanium Catalyst Co., Ltd. is produced (contains TiO
280%) 140g and crystalline aluminosilicate powder 60g add the blue or green powder 10g in field, mix.Alumina gel 100g is added in the aforesaid material, after fully mixed the pinching, on preceding crowded formula twin screw banded extruder, be extruded into the trifolium shape bar that equivalent diameter is 1.4mm, the gained bar that wets is 60 ℃ of dryings 2 hours, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 3 hours, get carrier D, its character sees Table 1, through the Mo-Co solution impregnation, through 110 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyzer D1, its character sees Table 2.
The titanium dioxide dry glue powder that Deqing branch office of Beijing Haishunde Titanium Catalyst Co., Ltd. is produced (contains TiO
280%) 80g, aluminum oxide dry glue powder 60g and crystalline aluminosilicate powder 60g add the blue or green powder 10g in field, mix.Alumina gel 110g is added in the aforesaid material, after fully mixed the pinching, on preceding crowded formula twin screw banded extruder, be extruded into the trifolium shape bar that equivalent diameter is 1.4mm, the gained bar that wets is 60 ℃ of dryings 2 hours, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 3 hours, get carrier E, its character sees Table 1, through the Mo-Co solution impregnation, through 110 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyzer E1, its character sees Table 2.
Comparative example 1
With the aluminum oxide dry glue powder 200g that research institute of Shandong Aluminium Industrial Corp produces, add the blue or green powder 10g in field, mix.Use 3%HNO
3Solution 50ml adds in the aforesaid material, after fully mixed the pinching, is extruded into the trifolium shape bar that equivalent diameter is 1.4mm on preceding crowded formula twin screw banded extruder, the gained bar that wets is dry 2 hours of 60 degree, dry 2 hours of 120 degree, 500 degree roastings 3 hours, get carrier F, its character sees Table 1, according to traditional Hydrobon catalyst prescription dipping Mo-Co solution, through 110 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyzer F1, its character sees Table 2.
Embodiment 6
The FCC gasoline that utilizes Cangzhou branch office of stock company of China Petrochemical Industry to produce carries out the desulfurating and reducing olefinic hydrocarbon benchmark test to above-mentioned catalyzer, stock oil character sees Table-3, evaluating apparatus is typical 100ml light oil hydrogenation reaction device, and loaded catalyst is 50ml here, and globule size is the disconnected bar of 2～5mm.Concrete appreciation condition sees Table-4, and 290 ℃ of temperature of reaction each routine evaluating catalyst result's contrast down see Table-5, and under the differential responses temperature, figure-1 shows catalyzer E1 hydrogenating desulfurization and falls relation between the alkene.From table-5, find out titanium base (TiO of the present invention
2Be carrier) catalyzer metal content be starkly lower than the tradition aluminium base (Al
2O
3Be carrier) catalyzer, reaction conditions compares under the demulcent situation, and hydrotreatment FCC gasoline is when generating the decline of oily sulphur content and olefin(e) centent, the former gasoline octane rating (RON) loss is 1 ~ 2 unit, and octane value (RON) loss that latter's aluminium-based catalyst is handled gasoline is 10 units.Shown the desulfuration selectivity that this catalyzer is good.
Table-1 carrier character
Table-2 catalyst properties
| Catalyzer | A1 | B1 | C1 | D1 | E1 | F1 |
| Carrier | A | B | C | D | E | F |
| Pore volume, ml/g | 0.38 | 0.38 | 0.38 | 0.36 | 0.43 | 0.42 |
| Specific surface, m 2/g | 175 | 160 | 155 | 210 | 232 | 202 |
| Intensity, N/ | 88 | 98 | 86 | 120 | 135 | 118 |
| MoO 3，w％ | 3.2 | 4.1 | 4.1 | 5.1 | 7.5 | 15.3 |
| CoO，w％ | 1.3 | 1.6 | 1.6 | 2.0 | 3.0 | 4.2 |
Table-3 stock oil character
| Density, g/ml | 0.7325 | Total sulfur, ppm | 1590 |
| Total nitrogen, | 30 | Alkene, v% | 45.8 |
| The bromine valency, gBr/100g | 84 | Aromatic hydrocarbons, v% | 23.0 |
| Research octane number (RON) (RON) | 91.9 | Motor-method octane number (MON) | 79.1 |
| Boiling range, ℃ | IBP 10％ 30％ 50％ 70％ 90％ EP 28 49 77 110 145 179 210 | ||
Table-4 appreciation conditions
| Reaction pressure, Mpa | 1.6 | Temperature of reaction, | 290 |
| Liquid air speed, h -1 | 4 | Hydrogen-oil ratio, v/v | 200 |
Table-5 each routine catalyst hydrogenation desulfurating and reducing olefinic hydrocarbon activity
Description of drawings
Relation between the relative range of decrease of desulfurization degree and alkene is seen figure-1
Claims (7)
1. gasoline hydrogenation catalyst, by the weight percent meter of described catalyzer, its component is:
Contain the TiO that consumption is 40～80w%
2And TiO
2-ZrO
2Perhaps TiO
2And TiO
2-SiO
2And surplus is the carrier of binding agent;
The A active ingredient is selected from CoO, NiO, and its content is 0.1～8w%;
The B active ingredient is selected from MoO
3, WO
3, its content is 1～13w%.
2. according to the described catalyzer of claim 1, it is characterized in that: the content of A active ingredient is 1～5w%.
3. according to the described catalyzer of claim 1, it is characterized in that: the content of the active group of B is 3～8w%.
4. according to the described catalyzer of claim 1, it is characterized in that: the TiO in the described carrier
2-ZrO
2Perhaps TiO
2-SiO
2In the oxide compound, TiO
2: ZrO
2Perhaps TiO
2: SiO
2Weight ratio be 3: 1.
5 according to the described catalyzer of claim 1, it is characterized in that: the TiO in the described carrier
2And TiO
2-ZrO
2Perhaps TiO
2And TiO
2-SiO
2Content is 60w%.
6. one kind according to the described Preparation of catalysts method of one of claim 1～5, the steps include:
Preparing carriers:;
(1) takes by weighing TiO
2And TiO
2-ZrO
2Perhaps TiO
2And TiO
2-SiO
2Powder, add and to contain Al
2O
3And/or SiO
2Binding agent mixes and pinched 10～40 minutes;
(2) by (1) gained material extruded moulding on banded extruder;
(3) by (2) gained material, under 60～140 ℃ of temperature, dry 1～5 hour;
(4) by (3) gained material, under 300～500 ℃ of temperature, roasting 2～5 hours;
The dipping active ingredient:
(5) with containing the excessive dipping of solution of molybdenum or tungsten and nickel and/or cobalt by (4) gained carrier;
(6) by (5) gained material, under 60～140 ℃ of temperature, dry 1～5 hour;
(7) by (6) gained material, under 350～500 ℃ of temperature, roasting 1～4 hour.
7. one kind according to the application of the described catalyzer of one of claim 1～5 in desulfurizing and reducing olefine for gasoline.
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| CN 02116267 CN1218021C (en) | 2002-03-28 | 2002-03-28 | Gasoline hydrogenation catalyst, its prep. and application in lowering olefin by desulfurization |
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|---|---|---|---|
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| CN1218021C true CN1218021C (en) | 2005-09-07 |
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Families Citing this family (6)
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|---|---|---|---|---|
| CN100345943C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Process for hydrodesulphurization and olefin reduction of gasoline |
| CN103131467B (en) * | 2011-12-01 | 2015-11-25 | 北京海顺德钛催化剂有限公司 | A kind of processing method of selectively hydrogenating and desulfurizing inferior gasoline and device |
| CN104338565B (en) * | 2013-08-09 | 2016-08-10 | 中国石油天然气股份有限公司 | Method for presulfurizing catalytic gasoline hydrogenation catalyst |
| CN106622358A (en) * | 2016-09-30 | 2017-05-10 | 过冬 | Composite support hydrodesulfurization catalyst |
| CN114433118B (en) * | 2020-10-30 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Ebullated bed hydrogenation catalyst and method for processing coal tar full fraction |
| CN114433119B (en) * | 2020-10-30 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Heavy aromatic oil hydrofining catalyst and method for producing BTX from heavy aromatic oil |
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