CN100548487C - A kind of aromatized eutectic superfine zeolite grain catalyst and its production and application - Google Patents
A kind of aromatized eutectic superfine zeolite grain catalyst and its production and application Download PDFInfo
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Abstract
The invention discloses a kind of aromatized eutectic superfine zeolite grain catalyst and preparation method thereof and fall application in the olefin process process in the catalytic gasoline of whole fraction hydrodesulfurization.This catalyst composed as follows: transition metal oxide content is 0.5wt%～10.0wt%, the lanthanide rare metal oxide content is 0.5wt%～5.0wt%, ultrafine particle eutectic zeolite content is 50.0wt%～90.0wt%, surplus is an inorganic oxide adhesive, and the grain size of ultrafine particle eutectic zeolite is 20nm～500nm.The ultrafine particle eutectic zeolite catalyst of the inventive method preparation is applied to can reduce FCC gasoline sulfur and olefin(e) centent significantly in FCC gasoline hydrodesulfurizationmethod/aromatisation group technology, and gasoline products anti-knock index ((R+M)/2) loss is less.Particularly compare with mechanical mixture ultrafine particle zeolite aromatized catalyst, the aromatized eutectic superfine zeolite grain catalyst coke content reduces more than 23%.
Description
1, technical field
The present invention relates to a kind of aromatized eutectic superfine zeolite grain catalyst and preparation method thereof and the application in catalytic gasoline of whole fraction hydrodesulfurization and aromatisation group technology.
2, background technology
The alkene and the sulfur content that reduce in the gasoline can effectively reduce exhaust of some harmful pollutants, and for this reason, what oneself had all been formulated in countries in the world turns to the clean gasoline new standard of sign with low-sulfur and low alkene.Sulfur content ≯ 50 μ the g/g of Europe IV class automobile exhaust emission standard (EU2005 standard) regulation gasoline after 2005, olefin(e) centent is 14v%～18v%; Sulfur content ≯ 80 μ the g/g of U.S. U.S.EPA Tier 2 standard codes U.S.'s clean gasoline after 2006, olefin(e) centent ≯ 14v%.The clean gasoline new standard Q/SHR010-2005 that China formulates requires the sulfur content ≯ 500 μ g/g of gasoline after 1 day July in 2005, olefin(e) centent ≯ 35.0v%.On July 1st, 2005, European III class automobile exhaust emission standard is carried out in Beijing, the sulfur content of gasoline ≯ 150 μ g/g, and olefin(e) centent is not more than 25.0v%.On July 1st, 2007 1, national standard is carried out European III discharge standard, and European IV discharge standard is carried out in Beijing, and on July 1st, 2010 1, national standard is carried out European IV discharge standard.The sulfur content and the olefin(e) centent of the following gasoline in countries in the world all can be more and more lower.
At present, catalytic cracking (FCC) gasoline shared large percentage in gasoline products, but catalytic cracking (FCC) sulfur in gasoline content and olefin(e) centent are higher.Therefore, the sulfur content of reduction catalytically cracked gasoline and olefin(e) centent are the keys that satisfies more and more stricter clean gasoline new spec.
Though adopt traditional hydrofining technology can remove sulfide and olefin(e) compound in the catalytically cracked gasoline effectively, but because the higher low-octane alkane of the saturated generation of hydrogenation of olefins of octane number, so, adopt traditional Hydrobon catalyst and technology when desulfurization and reducing olefin(e) centent, must follow the rapid decline of octane number.Generally, the desulfurization degree of catalytic gasoline is 90% o'clock, 5.0～8.0 units of anti-knock index ((R+M)/2) loss.Consume a large amount of hydrogen simultaneously.How reducing the saturated loss of octane number that causes of alkene is the difficult point of catalytic gasoline in hydrodesulfurization and reduction olefin(e) centent problem.
Because sulphur concentrates on than heavy distillat, alkene and concentrates on lighter fraction in the catalytically cracked gasoline.In the former document, propose many schemes and removed sulfide, kept the alkene that octane number is had positive contribution simultaneously.For example, US.Pat.No.3,759,821, US.Pat.No.4, the method for 062,762 disclosed upgrading catalytically cracked gasoline all is to be 2 kinds or 3 kinds of cuts with the catalytically cracked gasoline fractionation, every kind of cut diverse ways sulphur removal merges these cuts then.
U.S.Pat.5,362,376 technologies of having introduced a kind of catalyzed gasoline hydrogenation desulfurization and having selected shape hydrocracking two-stage catalytic agent combination.The catalytically cracked gasoline heavy distillat that is characterized in prefractionation is after hydrodesulfurization, pass through the NiO/HZSM-5 molecular sieve catalyst shape slective cracking of mesopore, acidity again, recovery is because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization, and then is in harmonious proportion with light fraction.U.S.Pat.No.5,413,698 have introduced two sections assembly catalyze gasoline desulfurs of another kind of hydrodesulfurization/octane value recovering new technology.Be characterized in that catalytic gasoline heavy distillat at first carries out desulfurization by a kind of conventional hydrodesulfurization Mo-Co or Mo-Ni catalyst, the desulfurization product process is by mesopore HZSM-5 zeolite and macropore HBeta zeolite mechanical impurity catalyst treatment preparation and the load nickel oxide then, low-octane alkane selective cracking or isomery are turned to high-octane hydro carbons, recovery is because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization, and then is in harmonious proportion with light fraction.
CN1151234C discloses the Catalysts and its preparation method that a kind of low-quality gasoline upgrading is produced clean gasoline.Thick cracking gasoline carries out upgrading containing on the little crystal grain HZSM-5 of rare-earth oxide, obtains the clean gasoline of low alkene, low-sulfur.Though, adopted the acid little crystal grain HZSM-5 carrier of hydrothermal treatment consists to reduce its acid strength and sour density in this patent application, this aromatized catalyst coking deactivation speed is very fast, and catalytic performance stability is not ideal enough.
CN1041399C discloses to synthesize and has contained rare earth and have ZSM-5 and the zeolite of ZSM-11 eutectic structure.Adopt X-ray polycrystal powder diffraction approach (XRD) to characterize that the weight ratio of ZSM-5 crystal phase structure part and ZSM-11 crystal phase structure part is 0.05～20 in this eutectic zeolite, the synthetic down former powder of anhydrous state is XNa with the chemical constitution formula of oxide mol ratio formal representation
2OYRE
2O
3Al
2O
3ZSiO
2, wherein X=0.1～1.0, Y=0.01～1.0, Z=20～300.ZL96106561.3 further illustrates this eutectic zeolite and is applied in the characteristics that have bigger activity, selectivity and activity stability in the benzene alkylation with ethylene catalyst.
Catalytically cracked gasoline contains the alkadienes of 0.5v%～5.0v% usually.At high temperature, alkadienes is easy to polymerization on the highly acid position on acid molecular sieve catalyst surface, causes the catalyst coking, slackens the catalytic activity of catalyst, reduces the stability of catalyst.Can make when serious between reactor inlet and the outlet and produce bigger pressure differential (abbreviation pressure drop), shorten the on-stream time of device.
CN1227334C discloses a kind of ultrafine particle zeolite aromatized catalyst, and this catalyst is to adopt ultrafine particle zeolite single or mechanical mixture to make.The aromatization of hydrocarbon molecules is undertaken by the carbonium ion reaction mechanism, need consecutive steps such as experience dehydrogenation, hydrogen migration, isomerization, cyclisation and alkylation, require catalyst to have proper acidic matter and enough geometric spaces (to see the catalysis journal, 26 (3): 216～222 (2005)).The catalyst acid character of single ultrafine particle zeolite preparation is single, therefore, is unfavorable for the reactions such as aromatisation of hydrocarbon molecules; The catalyst that the ultrafine particle zeolite of mechanical mixture is made, the crosslinked intercommunity in the duct of different size is poor, is unfavorable for the diffusion of hydrocarbon molecules, therefore, causes secondary responses such as polymerization easily, and catalyst carbon deposition speed is very fast, and stability of catalytic activity is not ideal enough.
3, summary of the invention
The objective of the invention is to propose a kind of aromatized eutectic superfine zeolite grain catalyst and preparation method thereof and fall the application in the alkene group technology in full cut FCC gasoline hydrodesulfurizationmethod, aromatisation.Its characteristics are under the situation that reduces FCC content of sulfur in gasoline and olefin(e) centent significantly, and the loss of octane number of the clean gasoline product of production is little, and particularly the catalyst anti-coking performance is strong, good stability.
A kind of aromatized eutectic superfine zeolite grain catalyst provided by the invention, weight with catalyst is benchmark, its composition comprises: transition metal oxide content is 0.5wt%～10.0wt%, the lanthanide rare metal oxide content is 0.5wt%～5.0wt%, ultrafine particle eutectic zeolite content is 50.0wt%～90.0wt%, surplus is an inorganic oxide adhesive, and the grain size of ultrafine particle eutectic zeolite is 20nm～500nm.
Above-mentioned transition metal oxide is one or more in zinc oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the tungsten oxide, particularly nickel oxide, molybdenum oxide and zinc oxide, the lanthanide rare metal oxide is lanthana and/or cerium oxide, particularly lanthana.
The specific area of above-mentioned ultrafine particle eutectic zeolite catalyst is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g.
Above-mentioned aromatized eutectic superfine zeolite grain catalyst pyridine weight adsorption is measured B acid, L acid and total acid content and is respectively: 0.020mmol/g～0.080mmol/g, 0.100mmol/g～0.2500mmol/g, 0.120mmol/g～0.330mmol/g.
Above-mentioned ultrafine particle eutectic zeolite can be selected from one or more among ZSM-5/ZSM-11, ZSM-5/ZSM-12, ZSM-5/M (modenite), ZSM-5/L, ZSM-5/Beta, ZSM-5/ZSM-22, the ZSM-5/ZSM-23, particularly ZSM-5/ZSM-11 and ZSM-5/Beta.
To account for weight ratio be 50%～90% to ZSM-5 in the above-mentioned ultrafine particle eutectic zeolite.
The hydrothermal synthesis method of above-mentioned ultrafine particle eutectic zeolite illustrates in many patent documentations and open source literature.Patent documentation such as US 4229424, US 5405596, and EP 130809, and EP 173901, CN1048655C, CN 1137022A, CN 1240193A, CN 1436726A, CN 1594088A etc.Periodical such as Zeolites 14 (1994), Micropor.Mesopor.Mater.43 (2001) 51-59 etc.
Above-mentioned ultrafine particle eutectic zeolite adopts X-ray polycrystal powder diffraction approach (XRD) and transmission electron microscopy (TEM) that zeolite crystal phase structure and zeolite grain degree size are measured respectively.
Described binding agent is titanium oxide, aluminium oxide, silica or aluminium oxide-silicon oxide.
The preparation method of aromatized eutectic superfine zeolite grain catalyst provided by the present invention may further comprise the steps:
A, ultrafine particle eutectic zeolite and binding agent are mixed, grind evenly, add aqueous solution of nitric acid, be rolled into extruded moulding after the wet cake of micelle shape, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～600 ℃ following roastings 3～10 hours, prepare aromatized eutectic superfine zeolite grain catalyst carrier intermediate;
B, the said catalyst carrier intermediate is packed in the activation furnace, be to be warming up to 500～600 ℃ under the atmosphere of 1: 1～10: 1 water vapours at water/solid volume ratio, and thermostatted water heat treatment 3～15 hours under this temperature, then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere that nitrogen content is 85wt%～95wt%, and the wet steam displacement of adsorbing on the catalyst is clean, after control is cooled to room temperature, draw off;
C, the sample of getting above-mentioned hydrothermal treatment consists are put into beaker, adding equivalent concentration in the ratio of water/solid volume than 2: 1～5: 1 is 0.10N～2.0N dilute inorganic acid solution, be 20～100 ℃ in temperature and stir rinsing 2～5 times down, then, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～500 ℃ following roastings 3～10 hours, prepare the aromatized eutectic superfine zeolite grain catalyst carrier;
D, with above-mentioned carrier incipient impregnation in the aqueous solution that contains transition metal 5～10 hours, then, drying is 8～15 hours under 110 ℃～140 ℃, 400 ℃～500 ℃ following roastings 3～10 hours, prepare the aromatized eutectic superfine zeolite grain catalyst that contains transition metal oxide and lanthanide rare metal oxide.
Wherein the lanthanide rare metal oxide is downloaded to mode in the catalyst and can adopts any method commonly used in the prior art, such as the method that adopts ion-exchange and/or dipping.Ion-exchange and dipping method can adopt method of the prior art, as follows such as ion exchange process: as to adopt the aqueous solution and the ultrafine particle eutectic zeolite that contain the lanthanide rare metal oxide to carry out the eutectic zeolite that ion-exchange formation contains rare earth, dipping process is as follows: adopt the solution impregnating catalyst carrier that contains the lanthanide rare metal oxide, can flood altogether with the aqueous solution that contains transition metal oxide, also can flood respectively with the aqueous solution that contains transition metal oxide.
Among the above-mentioned preparation method, the concentration 3.0～8.0g/100ml of the described nitric acid of step a, diluted mineral acid is watery hydrochloric acid, rare nitric acid, phosphoric acid,diluted or rare carbonic acid etc. among the step c, its equivalent concentration is 0.2～1.0N.
The aqueous solution of the above-mentioned aqueous solution that contains transition metal and lanthanide rare metal is normally formulated by its nitrate or sulfate.
Hydrodesulfurization, aromatisation that eutectic zeolite aromatized catalyst of the present invention can be applied to catalytic gasoline are fallen in the olefin process, thereby reach when desulfurization and reducing olefin(e) centent the purpose that the loss of octane number of product is less.This technology specific operation process is:
First section removing alkadiene by selective hydrogenation reaction: catalytic gasoline of whole fraction is contacted with hydrogenation catalyst under the hydrorefined condition that relaxes, partly to remove the sulfide in the gasoline, particularly to remove the diolefin of easy polymerization coking under the high temperature fully.
Second section aromatization: with the product process ultrafine particle zeolite eutectic aromatized catalyst of the present invention of first section selective hydrogenation, at reaction pressure 1.0MPa～3.5MPa, 340 ℃～420 ℃ of reaction temperatures, volume space velocity 0.5h
-1～3.0h
-1Under 200: 1～800: 1 condition of hydrogen to oil volume ratio, carry out aromatization, avoiding because of reducing the loss of the octane number that olefin(e) centent causes, isomerization of carrying out and cracking reaction simultaneously also played certain booster action to octane value recovering.
The 3rd section selective hydrodesulfurization reaction: second section aromatization reaction products contacted with catalyst for selectively hydrodesulfurizing under the condition of hydrodesulfurization, to remove the sulfide in the gasoline.
Said Hydrobon catalyst can be the Hydrobon catalyst of any routine, preferably MoO in first section
3-CoO/ aluminium oxide or WO
3-MoO
3-NiO/ aluminium oxide catalyst.Said hydrofinishing condition is: reaction pressure 1.0MPa～3.5MPa, 180 ℃～280 ℃ of reaction temperatures, volume space velocity 2.0h
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.
The catalyst for selectively hydrodesulfurizing that provides is provided in the 3rd section selective hydrodesulfurization can be conventional Hydrobon catalyst, by one or more base metals in group vib and/or the group VIII in the periodic table of elements is active component, with in amorphous alumina, siliceous aluminium oxide and the titanium-contained aluminum oxide one or more is carrier, preferably contain auxiliary agent, as in phosphorus, potassium, the fluorine one or more.
The used catalyst for selectively hydrodesulfurizing of the present invention preferably adopts a kind of highly active Hydrobon catalyst and a kind of SA Hydrobon catalyst at least, and adopts along the reactant flow path direction, and the active principle that reduces is gradually loaded; Wherein can adopt a kind of highly active Hydrobon catalyst and a kind of SA Hydrobon catalyst, wherein highly active Hydrobon catalyst is positioned at the upstream of SA Hydrobon catalyst, and its percent by volume is 30/70～70/30.
Metal oxide content is 8.0wt%～18.0wt%, particularly 10.0wt%～15.0wt% in the described highly active Hydrobon catalyst; Auxiliary agent content is 1.0wt%～5.0wt%, particularly 1.5wt%～3.0wt%; Metal oxide content is 1.0wt%～10.0wt%, particularly 3.0wt%～6.0wt% in the SA Hydrobon catalyst, and auxiliary agent content is 1.0wt%～5.0wt%, particularly 1.5wt%～3.0wt%.Described reactive metal is preferably one or more in cobalt, molybdenum, nickel, the tungsten.Auxiliary agent is one or more in phosphorus, potassium, the fluorine.High activity can adopt identical reactive metal with the low activity Hydrobon catalyst, also can adopt different reactive metals.This catalyst can adopt immersion process for preparing, can adopt step impregnation method, also can adopt and soak method altogether.Maceration extract can wait the adsorbance dipping, also can be the excessive dipping of maceration extract.
After the present invention adopted catalyst for selectively hydrodesulfurizing different activities combination loading, feedstock oil selective hydrogenation desulfurization process condition is: reaction pressure was generally 1.0MPa～3.5MPa, and reaction temperature is generally 230 ℃～330 ℃, and volume space velocity is generally 3.0h during liquid
-1～15.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; Reaction pressure is preferably 1.5MPa～3.0MPa, and reaction temperature is preferably 250 ℃～280 ℃, and volume space velocity is preferably 4.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is preferably 500: 1～and 700: 1.
The filling characteristics of Hydrobon catalyst system provided by the invention in reactor are that high activated catalyst is positioned at the upstream along the logistics direction, and low activity catalyst is positioned at the downstream.Hydrodesulfurization can produce a large amount of reaction heat, makes reactor downstream portion temperature higher (beds temperature rise), and industrial generally is to control the beds temperature rise by the method for injecting a large amount of cold hydrogen at the reactor middle part.The present invention will be placed on the downstream than the catalyst of low catalytic activity, can annotate cold hydrogen less, even not use cold hydrogen, realize avoiding under the high temperature hydrogenation excessive, and it is saturated to suppress hydrogenation of olefins, reduces the purpose of loss of octane number.
Three sections catalytic reactions of the present invention are operated under close pressure, can satisfy the needs of reaction system hydrogen circulation with same recycle compressor, help energy savings, and save equipment investment.
Catalyst of the present invention and technology not only can the production sulfur content be lower than the clean gasoline that 50 μ g/g, mercaptan sulfur are lower than 10 μ g/g, and clean gasoline product octane number does not lose substantially.
4, the specific embodiment
Comparative Examples 1
This Comparative Examples prepares 3.0wt%NiO-0.8wt%ZnO-4.0wt%La
2O
3(the HBeta/HZSM-5 percentage by weight is/HBeta+HZSM-5: aromatized catalyst 50/50).Wherein the HBeta grain size is 70nm～150nm; The HZSM-5 grain size is 90nm～500nm.
Take by weighing 118.8g HBeta (SiO
2/ Al
2O
3Mol ratio is 33), 106.0g HZSM-5 (SiO
2/ Al
2O
3Mol ratio is 27), 140.0g Al
2O
3, and their ground and mixed is even, adding 170ml concentration is the dilute nitric acid solution of 7.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 9 hours under 130 ℃, 520 ℃ of following roastings 6 hours, makes ultrafine particle HBeta+HZSM-5 zeolite Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, is to be warming up to 550 ℃ under 500ml/ hour the atmosphere of water vapour at water-flowing amount, and thermostatted water heat treatment 6 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyst is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of water/solid volume than 4: 1 is the dilute phosphoric acid solution of 0.40N, is 60 ℃ of slight down stirring rinsings 3 times in temperature.Then, 130 ℃ of dry down 8 hours, 470 ℃ following roastings 10 hours.Take out after reducing to room temperature, prepare ultrafine particle HBeta+HZSM-5 zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotary pump.In 30 minutes, 40ml contained 1.5g NiO, 0.4g ZnO and 2.0g La
2O
3Nickel nitrate, zinc nitrate and lanthanum nitrate hexahydrate spray in the catalyst carrier.After drying under the room temperature, 130 ℃ dry 9 hours down, 470 ℃ of following roastings 10 hours, make the ultrafine particle HBeta+HZSM-5 zeolite aromatized catalyst of nickeliferous, zinc and lanthanum, be numbered HBeta+HZSM-5.This catalyst rerum natura is listed in the table 1.
Example 1
This examples preparation 4.0wt%NiO-1.5wt%ZnO-1.5wt%La
2O
3/ grain size is 20nm～100nmHZSM-5/HZSM-11 eutectic zeolite aromatized catalyst.
Take by weighing 229.6g sodium type HZSM-5/HZSM-11 eutectic zeolite (SiO
2/ Al
2O
3Mol ratio is 27, and grain size is 20nm～100nm, and the weight ratio of HZSM-5 and HZSM-11 is 80: 20), 140.0g Al
2O
3, and their ground and mixed is even, adding 150ml concentration is the dilute nitric acid solution of 5.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 12 hours under 100 ℃, 500 ℃ of following roastings 10 hours, makes ultrafine particle HZSM-5/HZSM-11 Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, under the atmosphere of water flowing 150ml/ hour water vapour, be warming up to 510 ℃, and thermostatted water heat treatment 12 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyst is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of water/solid volume than 1.5: 1 is the dilute hydrochloric acid solution of 0.30N, is 40 ℃ of slight down stirring rinsings 4 times in temperature.Then, 100 ℃ of dry down 11 hours, 490 ℃ following roastings 6 hours.Take out after reducing to room temperature, prepare ultrafine particle HZSM-5/HZSM-11 eutectic zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotary pump.In 30 minutes, 35ml contained 2.0g NiO, 0.75g ZnO and 0.75g La
2O
3Nickel nitrate, zinc nitrate and lanthanum nitrate hexahydrate spray in the catalyst carrier.After drying under the room temperature, 100 ℃ dry 13 hours down, 490 ℃ of following roastings 6 hours, make the ultrafine particle eutectic zeolite HZSM-5/HZSM-11 aromatized catalyst of nickeliferous, zinc and lanthanum, be numbered HZSM-5/HZSM-11.This catalyst rerum natura is listed in the table 1.
Example 2
This examples preparation 6.0wt%MoO
3-2.0wt%CoO-3.0wt%La
2O
3/ grain size is 70nm～150nm HZSM-5/HBeta eutectic zeolite aromatized catalyst.
Take by weighing 239.6g HZSM-5/HBeta (SiO
2/ Al
2O
3Mol ratio is 33, and grain size is 70nm～150nm, and the weight ratio of HZSM-5 and HBeta is 60: 40), 140.0g Al
2O
3, and their ground and mixed is even, adding 180ml concentration is the dilute nitric acid solution of 3.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 510 ℃ of following roastings 8 hours, makes ultrafine particle HZSM-5/HBeta eutectic zeolite Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, is to be warming up to 520 ℃ under the atmosphere of 300ml/ hour water vapour at water-flowing amount, and thermostatted water heat treatment 10 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 85wt%, and the wet steam displacement of adsorbing on the catalyst is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of water/solid volume than 2.5: 1 is the dilute nitric acid solution of 0.45N, is 80 ℃ of slight down stirring rinsings 2 times in temperature.Then, 120 ℃ of dry down 9 hours, 480 ℃ following roastings 8 hours.Take out after reducing to room temperature, prepare ultrafine particle HZSM-5/HBeta eutectic zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotary pump.In 30 minutes, 45ml contained 3.0g MoO
3, 1.0g CoO and 1.5g La
2O
3The aqueous solution of ammonium molybdate, basic cobaltous carbonate and lanthanum nitrate spray in the catalyst carrier.After drying under the room temperature, drying is 10 hours under 110 ℃, 480 ℃ of following roastings 8 hours, makes the ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalyst that contains molybdenum, cobalt and lanthanum, is numbered HZSM-5/HBeta.This catalyst rerum natura is listed in the table 1.
Example 3
This examples preparation WO
37.0wt%-2.0wt%NiO-1.0wt%La
2O
3/ grain size is that 20nm～100nm contains rare earth ultrafine particle eutectic zeolite HZSM-5/HZSM-11 aromatized catalyst.
Take by weighing 229.6g and contain rare earth HZSM-5/HZSM-11 eutectic zeolite (La
2O
3Content is 1.0wt%, SiO
2/ Al
2O
3Mol ratio is 26, and grain size is 20nm～100nm, and the weight ratio of HZSM-5 and HZSM-11 is 70: 30), 140.0g Al
2O
3, and their ground and mixed is even, adding 150ml concentration is the dilute nitric acid solution of 5.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, 100 ℃ dry 12 hours down, 500 ℃ of following roastings 10 hours, make and contain rare earth ultrafine particle eutectic zeolite HZSM-5/HZSM-11 Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, under the atmosphere of water flowing 150ml/ hour water vapour, be warming up to 520 ℃, and thermostatted water heat treatment 10 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyst is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of water/solid volume than 1.5: 1 is the dilute hydrochloric acid solution of 0.30N, is 40 ℃ of slight down stirring rinsings 4 times in temperature.Then, 100 ℃ of dry down 11 hours, 490 ℃ following roastings 6 hours.Take out after reducing to room temperature, prepare and contain rare earth ultrafine particle eutectic zeolite HZSM-5/HZSM-11 Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotary pump.In 30 minutes, 35ml contained 3.5g WO
3Spray in the catalyst carrier with metatungstic acid and the nickel nitrate solution of 1.0g NiO.After drying under the room temperature, 100 ℃ dry 13 hours down, 490 ℃ of following roastings 6 hours, that makes nickeliferous, zinc and lanthanum contained rare earth ultrafine particle eutectic zeolite HZSM-5/HZSM-11 aromatized catalyst, is numbered RE-HZSM-5/HZSM-11.This catalyst rerum natura is listed in the table 1.
The rerum natura of table 1 zeolite aromatized catalyst
* the pyridine weight adsorption is measured: mmol/g
Comparative Examples 2
This example has provided the effect that Comparative Examples 1HZSM-5+HBeta zeolite aromatized catalyst is handled a kind of low sulfur content and medium olefin(e) centent FCC gasoline desulfur inferior and removal of mercaptans.
(1), first section removing alkadiene by selective hydrogenation reaction: 20ml commodity Hydrobon catalyst of packing in first reactor (trade names are FH-UDS, and Hua Hua Group Co.,Ltd in Wenzhou produces): WO
3(13.1wt%)-MoO
3(11.20wt%)-CoO (3.1wt%)-NiO (2.2wt%)/Al
2O
3
Reaction condition is: reaction pressure is 1.5MPa, and reaction temperature is 210 ℃, and the cumulative volume air speed is 6.0h
-1, hydrogen to oil volume ratio is 600: 1.
(2), second section aromatization: the 50ml HZSM-5+HBeta zeolite aromatized catalyst of packing in second reactor.
Reaction condition is: reaction pressure is 1.5MPa, and reaction temperature is 415 ℃, and the cumulative volume air speed is 2.5h
-1, hydrogen to oil volume ratio is 600: 1.
(3), the 3rd section selective hydrodesulfurization reaction: compare the 12.5ml high activity W O that packs into respectively with equal-volume in the 3rd reactor
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3Catalyst and a kind of low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyst.The former with the latter volume ratio is 50/50.
High activity W O
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3It is 189m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.46ml/g.
Low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3It is 282m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.57ml/g.
Reaction condition is: reaction pressure is 1.5MPa, and reaction temperature is 260 ℃, and the cumulative volume air speed is 7.0h
-1, hydrogen to oil volume ratio is 600: 1.
Table 2 has been listed the character of Comparative Examples 1 catalyst treatment FCC gasoline stocks and product.Turn round after 500 hours, stop work, draw off catalyst, measure HZSM-5+HBeta zeolite aromatized catalyst coke content.
The character of table 2 Comparative Examples 1 catalyst treatment FCC gasoline stocks and product
As can be seen from Table 2: method of the present invention can be reduced to 8 μ g/g by 300 μ g/g with the sulfur content of FCC gasoline, mercaptan sulfur content is reduced to 4.0 μ g/g by 50.5 μ g/g, olefin(e) centent is reduced to 17.0v% by 46.8v%, research octane number (RON) RON loses 2.2 units, anti-knock index (R+M)/2) 1.0 units of loss, C5+ yield of gasoline 95.2wt%.
Turn round after 500 hours, HZSM-5+HBeta zeolite aromatized catalyst coke content is 6.3wt%.
Example 4
Present embodiment has provided the effect that embodiment 1 ultrafine particle HZSM-5/HZSM-11 eutectic zeolite aromatized catalyst is handled a kind of moderate sulfur content and medium olefin(e) centent FCC gasoline desulfur inferior and removal of mercaptans.
(1), first section removing alkadiene by selective hydrogenation reaction: 20ml commodity Hydrobon catalyst of packing in first reactor (trade names are FH-98, and Hua Hua Group Co.,Ltd in Wenzhou produces): WO
3(20.0wt%)-MoO
3(9.0wt%)-NiO (4.5wt%)/Al
2O
3
Reaction condition is: reaction pressure is 1.6MPa, and reaction temperature is 200 ℃, and the cumulative volume air speed is 5.0h
-1, hydrogen to oil volume ratio is 600: 1.
(2), second section aromatization: the 50ml ultrafine particle HZSM-5/HZSM-11 eutectic zeolite aromatized catalyst of packing in second reactor.
Reaction condition is: reaction pressure is 1.6MPa, and reaction temperature is 405 ℃, and the cumulative volume air speed is 2.0h
-1, hydrogen to oil volume ratio is 600: 1.
(3), the 3rd section selective hydrodesulfurization reaction: compare the 12.5ml high activity W O that packs into respectively with equal-volume in the 3rd reactor
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3Catalyst and a kind of low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyst.The former with the latter volume ratio is 50/50.
High activity W O
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3It is 189m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.46ml/g.
Low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3It is 282m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.57ml/g.
Reaction condition is: reaction pressure is 1.6MPa, and reaction temperature is 270 ℃, and the cumulative volume air speed is 8.0h
-1, hydrogen to oil volume ratio is 600: 1.
Table 3 has been listed the character of example 1 catalyst treatment FCC gasoline stocks and product.Turn round after 500 hours, stop work, draw off catalyst, measure ultrafine particle HZSM-5/HZSM-11 eutectic zeolite aromatized catalyst coke content.
The character of table 3 example 1 catalyst treatment FCC gasoline stocks and product
As can be seen from Table 3: method of the present invention can be reduced to 30 μ g/g by 806 μ g/g with the sulfur content of FCC gasoline, mercaptan sulfur content is reduced to 6.0 μ g/g by 58.5 μ g/g, olefin(e) centent is reduced to 16.0v% by 40.3v%, research octane number (RON) RON loses 1.9 units, anti-knock index (R+M)/2) 0.9 unit of loss, C
5 +Yield of gasoline 97.2wt% can be processed as the high-quality cleaning products with the full distillation gasoline of FCC inferior.
Turn round after 500 hours, ultrafine particle HZSM-5/ZSM-11 eutectic zeolite aromatized catalyst coke content is 4.2wt%.
Example 5
Present embodiment has provided the effect that embodiment 2 ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalysts are handled a kind of high sulfur content and high olefin content FCC gasoline desulfur inferior and removal of mercaptans.
(1), first section removing alkadiene by selective hydrogenation reaction: 20ml commodity Hydrobon catalyst of packing in first reactor (trade names are FGH-11, and Hua Hua Group Co.,Ltd in Wenzhou produces): MoO
3(15.0wt%)-CoO (4.0wt%)/Al
2O
3
Reaction condition is: reaction pressure is 2.6MPa, and reaction temperature is 230 ℃, and the cumulative volume air speed is 8.0h
-1, hydrogen to oil volume ratio is 600: 1.
(2), second section aromatization: the 55ml ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalyst of packing in second reactor.
Reaction condition is: reaction pressure is 2.6MPa, and reaction temperature is 390 ℃, and the cumulative volume air speed is 2.9h
-1, hydrogen to oil volume ratio is 600: 1.
(3), the 3rd section selective hydrodesulfurization reaction: 27.0ml high activity MoO packs in the 3rd reactor
3(12.0wt%)-CoO (4.0wt%)-P
2O
5(1.5wt%)/Al
2O
3Catalyst and a kind of low activity MoO
3(3.0wt%)-NiO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyst.The former with the latter volume ratio is 70/30.
High activity MoO
3(12.0wt%)-CoO (4.0wt%)-P
2O
5(1.5wt%)/Al
2O
3It is 190m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.48ml/g.
Low activity MoO
3(3.0wt%)-NiO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3It is 298m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.59ml/g.
Reaction condition is: reaction pressure is 2.6MPa, and reaction temperature is 260 ℃, and the cumulative volume air speed is 5.9h
-1, hydrogen to oil volume ratio is 600: 1.
Table 4 has been listed the character of example 2 catalyst treatment FCC gasoline stocks and product.Turn round after 500 hours, stop work, draw off catalyst, measure ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalyst coke content.
The character of table 4 example 2 catalyst treatment FCC gasoline stocks and product
As can be seen from Table 4: method of the present invention can be reduced to 46 μ g/g by 1200 μ g/g with the sulfur content of FCC gasoline, mercaptan sulfur content is reduced to 6.0 μ g/g by 54.5 μ g/g, olefin(e) centent is reduced to 16.0v% by 45.9v%, research octane number (RON) RON loses 1.6 units, anti-knock index (R+M)/2) 0.9 unit of loss, C5+ yield of gasoline 96.5wt% can be processed as the high-quality cleaning products with the full distillation gasoline of FCC inferior.
Turn round after 500 hours, ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalyst coke content is 4.8wt%.
Example 6
This example has provided example 3 and has contained the effect that rare earth ultrafine particle eutectic zeolite HZSM-5/HZSM-11 aromatized catalyst is handled a kind of moderate sulfur content and medium olefin(e) centent FCC gasoline desulfur inferior and removal of mercaptans.
(1), first section removing alkadiene by selective hydrogenation reaction: 20ml commodity Hydrobon catalyst of packing in first reactor (trade names are FH-98, Wenzhou Hua Hua Group Co.,Ltd): WO
3(20.0wt%)-MoO
3(9.0wt%)-NiO (4.5wt%)/Al
2O
3
Reaction condition is: reaction pressure is 3.0MPa, and reaction temperature is 180 ℃, and the cumulative volume air speed is 5.0h
-1, hydrogen to oil volume ratio is 600: 1.
(2), second section aromatization: the 50ml ultrafine particle RE-HZSM-5/HZSM-11 eutectic zeolite aromatized catalyst of packing in second reactor.
Reaction condition is: reaction pressure is 3.0MPa, and reaction temperature is 400 ℃, and the cumulative volume air speed is 2.0h
-1, hydrogen to oil volume ratio is 600: 1.
(3), the 3rd section selective hydrodesulfurization reaction: compare the 12.5ml high activity W O that packs into respectively with equal-volume in the 3rd reactor
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3Catalyst and a kind of low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyst.The former with the latter volume ratio is 50/50.
High activity W O
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3It is 189m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.46ml/g.
Low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3It is 282m that catalyst adopts cryogenic nitrogen absorption BET method to measure specific surface area of catalyst
2/ g, pore volume are 0.57ml/g.
Reaction condition is: reaction pressure is 3.0MPa, and reaction temperature is 260 ℃, and the cumulative volume air speed is 9.0h
-1, hydrogen to oil volume ratio is 600: 1.
Table 5 has been listed the character of example 3 catalyst treatment FCC gasoline stocks and product.Turn round after 500 hours, stop work, draw off catalyst, measure ultrafine particle RE-HZSM-5/HZSM-11 eutectic zeolite aromatized catalyst coke content.
The character of table 5 example 3 catalyst treatment FCC gasoline stocks and product
As can be seen from Table 5: method of the present invention can be reduced to 38 μ g/g by 806 μ g/g with the sulfur content of FCC gasoline, mercaptan sulfur content is reduced to 6.8 μ g/g by 58.5 μ g/g, olefin(e) centent is reduced to 17.0v% by 40.3v%, research octane number (RON) RON loses 2.0 units, anti-knock index (R+M)/2) 1.0 units of loss, C
5 +Yield of gasoline 98.0wt% can be processed as the high-quality cleaning products with the full distillation gasoline of FCC inferior.
Turn round after 500 hours, ultrafine particle RE-HZSM-5/ZSM-11 eutectic zeolite aromatized catalyst coke content is 4.5wt%.
The above results shows, adopt the ultrafine particle eutectic zeolite catalyst of method preparation of the present invention to be applied in FCC gasoline hydrodesulfurizationmethod/aromatisation group technology, can reduce FCC gasoline sulfur and olefin(e) centent significantly, gained gasoline products not only total sulfur content is lower than 50 μ g/g, mercaptan sulfur content is lower than 10 μ g/g, and the loss of its product research method octane number (RON) is less than 2.0 units, and anti-knock index ((R+M)/2) loses less than 1.0 units.Particularly compare with mechanical mixture HZSM-5+HBeta ultrafine particle zeolite aromatized catalyst, turn round after 500 hours, ultrafine particle HZSM-5/HBeta eutectic zeolite aromatized catalyst coke content reduces more than 23%.
Claims (20)
1, a kind of aromatized eutectic superfine zeolite grain catalyst, weight with catalyst is benchmark, it consists of: transition metal oxide content is 0.5wt%～10.0wt%, the lanthanide rare metal oxide content is 0.5wt%～5.0wt%, ultrafine particle eutectic zeolite content is 50.0wt%～90.0wt%, surplus is an inorganic oxide adhesive, and the grain size of ultrafine particle eutectic zeolite is 20nm～500nm.
2,, it is characterized in that described ultrafine particle eutectic zeolite is selected from one or more among ZSM-5/ZSM-11, ZSM-5/ZSM-12, ZSM-5/M, ZSM-5/L, ZSM-5/Beta, ZSM-5/ZSM-22, the ZSM-5/ZSM-23 according to the described catalyst of claim 1.
3, according to the described catalyst of claim 2, it is characterized in that described ultrafine particle eutectic zeolite be among ZSM-5/ZSM-11 and the ZSM-5/Beta one or both.
4,, it is characterized in that in the described ultrafine particle eutectic zeolite that it is 50%～90% that ZSM-5 accounts for weight ratio according to claim 2 or 3 described catalyst.
5,, it is characterized in that in the described ultrafine particle eutectic zeolite that it is 60%～90% that ZSM-5 accounts for weight ratio according to the described catalyst of claim 4.
6, according to the described catalyst of claim 1, it is characterized in that described transition metal oxide is one or more in zinc oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the tungsten oxide, the lanthanide rare metal oxide is lanthana and/or cerium oxide.
7, according to the described catalyst of claim 1, it is characterized in that described transition metal oxide is one or more in nickel oxide, molybdenum oxide and the zinc oxide, the lanthanide rare metal oxide is a lanthana.
8, according to the described catalyst of claim 1, the specific area that it is characterized in that described ultrafine particle eutectic zeolite catalyst is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g, and B acid, L acid and total acid content are respectively: 0.020mmol/g～0.080mmol/g, 0.100mmol/g～0.2500mmol/g, 0.120mmol/g～0.330mmol/g.
9, the arbitrary described Preparation of catalysts method of claim 1～8 may further comprise the steps:
A, ultrafine particle eutectic zeolite and binding agent are mixed, grind evenly, add aqueous solution of nitric acid, be rolled into extruded moulding after the wet cake of micelle shape, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～600 ℃ following roastings 3～10 hours, prepare aromatized eutectic superfine zeolite grain catalyst carrier intermediate;
B, the said catalyst carrier intermediate being packed in the activation furnace, is to be warming up to 500～600 ℃ under the atmosphere of 1: 1～10: 1 water vapours at water/solid volume ratio, and thermostatted water heat treatment 3～15 hours under this temperature;
C, in the sample of above-mentioned hydrothermal treatment consists, adding equivalent concentration in the ratio of water/solid volume than 2: 1～5: 1 is 0.10N～2.0N dilute inorganic acid solution, in temperature is 20～100 ℃ of stirring, rinsings down, then, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～500 ℃ following roastings 3～10 hours, prepare the aromatized eutectic superfine zeolite grain catalyst carrier;
D, with above-mentioned carrier incipient impregnation in the aqueous solution that contains transition metal 5～10 hours, then, drying is 8～15 hours under 110 ℃～140 ℃, 400 ℃～500 ℃ following roastings 3～10 hours, wherein, the method that the metal oxide supported mode in catalyst of lanthanide rare is ion-exchange and/or dipping is prepared the aromatized eutectic superfine zeolite grain catalyst that contains transition metal oxide and lanthanide rare metal oxide.
10, according to the described preparation method of claim 9, it is characterized in that described ion exchange process is as follows: adopt the aqueous solution and the ultrafine particle eutectic zeolite that contain the lanthanide rare metal oxide to carry out the eutectic zeolite that ion-exchange formation contains rare earth; Described dipping process is as follows: adopt and soak altogether with the aqueous solution that contains transition metal oxide or divide the method for soaking that the lanthanide rare metal oxide is downloaded on the catalyst carrier.
11, the arbitrary described catalyst of claim 1～8 falls application in the olefin process at catalyzed gasoline hydrogenation desulfurization, and specific operation process is:
First section removing alkadiene by selective hydrogenation reaction: catalytic gasoline of whole fraction is contacted with hydrogenation catalyst under the hydrorefined condition that relaxes, partly to remove the sulfide in the gasoline, particularly to remove the alkadienes of easy polymerization coking under the high temperature fully;
Second section aromatization: the arbitrary described ultrafine particle zeolite eutectic aromatized catalyst of the product and the claim 1～8 of first section selective hydrogenation is contacted, carry out aromatization;
The 3rd section selective hydrodesulfurization reaction: second section aromatization reaction products contacted with catalyst for selectively hydrodesulfurizing under the condition of hydrodesulfurization, to remove the sulfide in the gasoline.
12,, it is characterized in that said Hydrobon catalyst is MoO in first section according to the described application of claim 11
3-CoO/ aluminium oxide or WO
3-MoO
3-NiO/ aluminium oxide catalyst; Said hydrofinishing condition is: volume space velocity 2.0h when reaction pressure 1.0MPa～3.5MPa, 180 ℃～280 ℃ of reaction temperatures, liquid
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.
13, according to the described application of claim 11, it is characterized in that second section aromatization condition is as follows: volume space velocity 0.5h when reaction pressure 1.0MPa～3.5MPa, 340 ℃～420 ℃ of reaction temperatures, liquid
-1～3.0h
-1With hydrogen to oil volume ratio 200: 1～800: 1.
14, according to the described application of claim 11, it is characterized in that the 3rd section used catalyst for selectively hydrodesulfurizing is is active component with one or more base metals in group vib and/or the group VIII in the periodic table of elements, with in amorphous alumina, siliceous aluminium oxide and the titanium-contained aluminum oxide one or more is carrier, and selectivity contains one or more in auxiliary agent phosphorus, potassium, the fluorine.
15, according to the described application of claim 11, it is characterized in that described catalyst for selectively hydrodesulfurizing adopts a kind of highly active Hydrobon catalyst and a kind of SA Hydrobon catalyst at least, and adopt along the reactant flow path direction, the active principle that reduces is gradually loaded.
16, according to the described application of claim 15, it is characterized in that described catalyst for selectively hydrodesulfurizing adopts a kind of highly active Hydrobon catalyst and a kind of SA Hydrobon catalyst, wherein highly active Hydrobon catalyst is positioned at the upstream of SA Hydrobon catalyst, and its percent by volume is 30/70～70/30.
17, according to claim 15 or 16 described application, it is characterized in that metal oxide content is 8.0wt%～18.0wt% in the described highly active Hydrobon catalyst, auxiliary agent content is 1.0wt%～5.0wt%; Metal oxide content is 1.0wt%～10.0wt% in the SA Hydrobon catalyst, and auxiliary agent content is 1.0wt%～5.0wt%; Described reactive metal is one or more in cobalt, molybdenum, nickel and the tungsten; Auxiliary agent is one or more in phosphorus, potassium, the fluorine.
18,, it is characterized in that metal oxide content is 10.0wt%～15.0wt% in the described highly active Hydrobon catalyst according to the described application of claim 17; Auxiliary agent content is 1.5wt%～3.0wt%; Metal oxide content is 3.0wt%～6.0wt% in the SA Hydrobon catalyst, and auxiliary agent content is 1.5wt%～3.0wt%.
19, according to claim 15 or 16 described application, it is characterized in that described selective hydrogenation desulfurization process condition is: reaction pressure is 1.0MPa～3.5MPa, and reaction temperature is 230 ℃～330 ℃, and volume space velocity is 3.0h during liquid
-1～15.0h
-1, hydrogen to oil volume ratio is 200: 1～1000: 1.
20, according to claim 15 or 16 described application, it is characterized in that described selective hydrogenation desulfurization process condition is: reaction pressure is 1.5MPa～3.0MPa, and reaction temperature is 250 ℃～280 ℃, and volume space velocity is 4.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is 500: 1～700: 1.
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| CN101898148B (en) * | 2009-05-27 | 2012-03-07 | 中国石油天然气股份有限公司 | L molecular sieve-containing catalytic gasoline selective hydrodesulfurization modification catalyst |
| CN102372535B (en) * | 2010-08-23 | 2014-05-28 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon through methanol transformation |
| CN102372550A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon through methanol transformation |
| CN102371176B (en) * | 2010-08-23 | 2013-06-19 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon through methanol conversion and preparation method thereof |
| CN102371177B (en) * | 2010-08-23 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof |
| CN102371178B (en) * | 2010-08-23 | 2013-10-16 | 中国石油化工股份有限公司 | Catalyst for preparing arene by methanol conversion and preparation method thereof |
| CN102153105A (en) * | 2010-12-31 | 2011-08-17 | 华东师范大学 | Method for preparing MFI/MEL (Mobil Fifth/Mobil Eleven) eutectic molecular sieve |
| CN103030490A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing ethylene through ethanol dehydration |
| CN103030486A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for manufacturing aromatic hydrocarbon from methanol |
| CN104549141B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Hetero-atom molecular-sieve adsorbent and preparation method thereof |
| CN108479846B (en) * | 2018-02-08 | 2019-12-31 | 中国石油大学(北京) | Aromatization catalyst, preparation method, regeneration method and aromatization method thereof |
| CN108435235B (en) * | 2018-03-26 | 2021-01-05 | 福州大学 | Mesoporous Zn-ZSM-5 molecular sieve and low-cost preparation method thereof |
| CN109097096B (en) * | 2018-09-11 | 2020-07-07 | 福州大学 | Method for pre-hydrogenation of catalytic cracking gasoline |
| CN111068767B (en) * | 2018-10-18 | 2023-01-10 | 中国石油化工股份有限公司 | Catalyst for producing clean gasoline and preparation and application thereof |
| CN109847793B (en) * | 2019-01-11 | 2021-12-10 | 中国石油大学(华东) | Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method |
| CN112063414B (en) * | 2019-06-10 | 2021-12-07 | 中国石油化工股份有限公司 | Up-flow residual oil hydrogenation reaction system and residual oil hydrotreating method |
| US11648540B2 (en) * | 2021-01-25 | 2023-05-16 | China Energy Investment Corporation Limited | Modified catalyst, method for preparing the same, and method for producing aromatic hydrocarbons by aromatization of olefins |
| CN114522718B (en) * | 2022-02-18 | 2024-05-07 | 山东明化新材料有限公司 | Preparation of ZSM-5/BEA co-crystallized molecular sieve catalyst and application of catalyst in preparation process of 3-methylpyridine |
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