CN102079996A - Catalytic conversion method for producing high-quality light fuels from crude oil - Google Patents
Catalytic conversion method for producing high-quality light fuels from crude oil Download PDFInfo
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Abstract
The invention discloses a catalytic conversion method for producing high-quality light fuels from crude oil. The crude oil contacts and reacts with a catalyst which is rich in mesoporous zeolite and in coarse particle size distribution. The catalytic conversion method is characterized in that a reaction product containing catalytic wax oil which accounts for 12-60 wt% of the weight of raw material is obtained by the reaction temperature, weight hourly space velocity and the weight ratio of raw oil to catalyst, wherein the reaction temperature is 420-600 DEG C, the weight hourly space velocity is 25-100 hours<-1>, the weight ratio of catalyst to raw oil is 1 to 30, and the wax is catalyzed before hydrocracks. In the invention, crude oil catalytic converter and hydrocracking methods are provided, which, in particular, reduces dry gas and coke yield significantly while converting the poor quality of crude oil into high octane gasoline and high-cetane diesel fuel so as to achieve efficient use of oil resources, and reduce the broken tendency of the catalyst and the catalyst consumption.
Description
Technical field
The present invention relates to the method for a kind of crude oil catalyzed conversion and hydrocracking combinations produce high-quality light Fuel.More specifically, be the method for producing stop bracket gasoline and high hexadecane value diesel oil substantially by catalyzed conversion and hydrocracking.
Background technology
Demand to high-quality diesel oil in worldwide increases day by day, to the then minimizing day by day of demand of oil fuel.Though vapour, diesel oil increase in demand are different and different with the area, generally worldwide will be above to the gasoline demand rate of growth to diesel oil growth of requirement speed.Therefore, more low-cetane catalysis solar oil just is being used to the blend component as diesel oil.And, need carry out upgrading to the catalysis solar oil in order to satisfy the demand of high-quality diesel oil, perhaps directly produce a large amount of high-quality catalysis solar oils by catalytic cracking (FCC).
The production of catalytically cracked gasoline and diesel oil generally is to be raw material and to mix refining part residual oil such as normal pressure residual oil (AR), vacuum residuum (VR) etc. with straight run vacuum distillate (VGO).Heavy metal content height such as the contained carbon residue of heavy feed stocks such as residual oil, sulphur, nitrogen, nickel, vanadium.For improving the character of these catalytic cracking unit (FCCU) charging, except by delayed coking or diasphaltene etc. to its decarburization, demetalization, the increasing employing of catalytic cracking makes FCCU stock oil increase hydrogen and depickling demetalization to heavy oil, residual hydrogenation, further fully efficiently utilizes crude oil.The hydro-upgrading hydrogen-consuming volume of FCCU charging is big, limited by hydrogen source, and FCCU charging hydrogenation can not overcome the drawback that sedimentation of coke causes catalyst activity and selectivity to descend in the conventional riser catalytic cracking process.Inherent defect at riser reactor, US4243514, US4263128 have disclosed the method for crude oil full-fraction or part fraction upgrading, adopt the inert heat carrier material absorption crude oil full-fraction or the part cut of no cracking activity, to remove carbon residue and the heavy metal in the raw material, the raw material behind the upgrading is re-used as the charging of conventional FCCU and carries out cracking.But many drawbacks such as gasoline property is poor, energy consumption height that this method exists.
Generally speaking, existing light fractions of FCC naphtha olefin(e) centent height, thereby the last running part octane value quality of gasoline that influences on the low side; Catalytic cracking diesel oil contains more mononuclear aromatics, and cetane value is low, and is second-rate.In order to satisfy the demand of growing motor spirit, be necessary to develop a kind of catalysis conversion method that heavy feed stock is converted into stop bracket gasoline and high-quality light Fuels such as high hexadecane value diesel oil and rocket engine fuel.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of catalysis conversion method of crude production high-quality light Fuel.
The catalysis conversion method of crude production high-quality light Fuel provided by the invention comprises:
In catalytic conversion reactor, with pre-treatment crude oil is that catalyzer that stock oil directly distributes with the coarse grain that contains large pore zeolite in reactor contacts and reacts, it is characterized in that temperature of reaction, the oil gas residence time, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, wherein said weight hourly space velocity is 25～100h
-1, described temperature of reaction is 420～600 ℃, described catalyzer and stock oil weight ratio are 1～30.Catalytic wax oil is further hydrocracking again.
Described temperature of reaction is 420～600 ℃, preferably, and 450～550 ℃, more preferably, 460～520 ℃.
Described weight hourly space velocity is 30～80h
-1, preferably, 40～60h
-1
The weight ratio of described catalyzer and stock oil is 1～30, preferably, and 2～25, more preferably, 3～14.
In embodiments, reaction pressure is 0.10MPa～1.0MPa.
Crude oil of the present invention is selected from or comprises in petroleum base crude oil and/or other mineral oil mixture of one or more (comprise two kinds, down with), and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
Crude Oil Pretreatment process of the present invention is meant processes such as conventional crude oil desalting, dehydration, decalcification, removes most salts substances (as magnesium chloride, sodium-chlor etc.), water and calcium etc. in the crude oil through said process.Of the present invention in pretreated crude oil vanadium, nickel total value preferably be not more than 30ppm, its density (20 ℃) is greater than 0.85gcm
-3, be preferably greater than 0.90gcm
-3, more preferably greater than 0.92gcm
-3
In preferred embodiments, described crude oil is selected from or comprises petroleum base crude oil, comprises in paraffinic crude, paraffin-intermediate base crude oil, centre-paraffinic crude, intermediate base crude oil, centre-naphthenic base crude, cycloalkanes-intermediate base crude oil, the naphthenic base crude one or more.Most preferred crude oil is petroleum base crude oil, more preferably contains the heavy crude base crude oil of at least 1 weight % pitch composition.
In embodiments, described catalyzer comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %.Its mesolite is large pore zeolite and/or optional mesopore zeolite, and large pore zeolite accounts for 80～100 heavy % of zeolite gross weight, the heavy % of preferred 90 heavy %-100; Mesopore zeolite accounts for 0～20 heavy % of zeolite gross weight, the heavy % of preferred 0 heavy %-10.Large pore zeolite is selected from the Y series zeolite, comprises super steady Y, high silicon Y that Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).In butt, the heavy % in silica comprises 50 heavy～90 in the inorganic oxide, aluminium sesquioxide accounts for the heavy % in 10 heavy～50.
Clay is as matrix (being carrier), is selected from silicon-dioxide, kaolin and/or halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Catalytic converting catalyst in each reactor can be identical, also can be different.
The size composition of the catalyzer that described coarse grain directly distributes is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, be preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
In a more preferred embodiment, described stock oil is introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than a position.
In a more preferred embodiment, described method also comprises separates reaction product with catalyzer, and catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises stop bracket gasoline, high hexadecane value diesel oil and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut.
In a more preferred embodiment, described catalytic wax oil hydrogen richness is not less than 11.5 heavy %, preferably is not less than 12 heavy %.
The catalytic wax oil hydrocracking is under there is situation in hydrogen, contacts with hydrocracking catalyst, at reaction pressure 4.0～16.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～10.0h
-1Reaction conditions under to carry out hydrocracking resultant.Hydrocracking tail oil can return catalytic convention design as stock oil.
The catalytic wax oil hydrocracking catalyst contains one or more active metal components among W, Mo, Ni and the Co, and acid cracking component.The weight content of active metal component in catalyzer is generally 5～50% in the hydrocracking catalyst, is generally 15～30%.Hydrocracking catalyst is for producing the intermediate distillates type hydrocracking catalyst of intermediate oil.Acid cracking activity component generally is selected from molecular sieve and amorphous silicon aluminium, and often the molecular sieve type that uses has: Y zeolite, beta molecular sieve, type ZSM 5 molecular sieve, SAPO series molecular sieve, or the like.Simultaneously can also contain other refractory inorganic oxides in the hydrocracking catalyst, as the composite oxides of aluminum oxide, silicon oxide, titanium oxide and various elements or mixed oxide etc.
The preparation method of catalytic wax oil hydrocracking catalyst comprises molecular sieve preparation and preparing carriers.The preparation of molecular sieve comprises the synthetic and modification of molecular sieve, and modification mainly contains metallic cation exchange, hydrothermal treatment consists, liquid phase chemical modification, gas chemistry modification etc.The preparation of carrier has extrusion method and coprecipitation method.
Preferred forms of the present invention is to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
In another embodiment of the invention, providing a kind of is the catalysis conversion method of stock oil with pretreated crude oil such as desalination, dehydrations, and wherein stock oil contacts with the catalyzer that is rich in large pore zeolite in reactor and reacts, and it is characterized in that:
(1) stock oil comprises difficult cracking stock oil and easy cracking stock oil, a position described stock oil is introduced in the reactor, or in the position of identical or different height more than described stock oil is introduced in the reactor;
(2) the catalyzer contact reacts that in reactor, directly distributes with the coarse grain that is rich in large pore zeolite earlier of difficult cracking stock oil, or be not later than easy cracking stock oil and react;
(3) temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil;
(4) reclaimable catalyst separates by cyclonic separator with reaction oil gas; Randomly, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration; Reaction oil gas obtains comprising the reaction product of stop bracket gasoline, high hexadecane value diesel oil, catalytic wax oil through separation;
(5) wherein catalytic wax oil obtains gasoline, high hexadecane value diesel oil and hydrogenation heavy oil through hydrocracking, and described hydrogenation heavy oil is oily or/and easy cracking stock oil turns back to step (1) or/and in the step (2) as difficult cracking stock.
Described difficult cracking stock grease separation from or comprise that density (20 ℃) is greater than 0.90gcm
-3Be preferably greater than 0.92gcm
-3More preferably greater than 0.93gcm
-3Crude oil with poor quality, slurry oil, diesel oil, gasoline in one or more mixture.Described gasoline be selected from or comprise present method gained catalytically cracked gasoline, from a kind of in the outer catalytically cracked gasoline of this device, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, the hydrogenated gasoline or more than one mixture wherein, wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from this device gasoline outward.Described diesel oil is selected from or comprises a kind of in present method gained catalytic cracking diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, the hydrogenated diesel oil or more than one mixture wherein, and wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.
Described easy cracking stock grease separation from or comprise through the pretreated petroleum base crude oil of routine and/or other mineral oil.Wherein petroleum base oil density (20 ℃) is greater than 0.85gcm
-3, but be not higher than 0.90gcm
-3, can be selected from one or more the mixture in paraffinic crude, paraffin-intermediate base crude oil, centre-paraffinic crude, intermediate base crude oil, centre-naphthenic base crude, cycloalkanes-intermediate base crude oil, the naphthenic base crude; Other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
The reaction conditions of difficult cracking stock oil is: 520～650 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is 0.05～1.0.
Easily the reaction conditions of cracking stock oil is: 420～550 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1.0～30 of cracking stock oil, water vapor is 0.05～1.0 with the easy weight ratio of cracking stock oil.Preferably, easily the temperature of reaction of cracking stock oil is 450～540 ℃, and weight hourly space velocity is 10～90h
-1, be preferably 20～60h
-1More preferably, easily the temperature of reaction of cracking stock oil is 460～520 ℃, weight hourly space velocity 30～50h
-1, catalyzer and stock oil weight ratio are 3～14.
In the present embodiment, the separation of catalyzer, reactor and reaction product etc. are identical with preceding a kind of embodiment.
The size composition of the catalyzer that described coarse grain directly distributes is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, be preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
In order to increase the agent-oil ratio of reaction catchment, improve the catalytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7; The reclaimable catalyst carbon content is more than the 0.9 heavy %, and preferably carbon content is the heavy % in 0.9 heavy %～1.2.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut.
In a more preferred embodiment, described catalytic wax oil hydrogen richness is not less than 11.5 heavy %, preferably is not less than 12 heavy %.
The catalytic wax oil hydrocracking is under there is situation in hydrogen, contacts with hydrocracking catalyst, at reaction pressure 4.0～16.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～10.0h
-1Reaction conditions under to carry out hydrocracking resultant.Hydrocracking tail oil can return catalytic convention design as stock oil.
The catalytic wax oil hydrocracking catalyst contains one or more active metal components among W, Mo, Ni and the Co, and acid cracking component.The weight content of active metal component in catalyzer is generally 5～50% in the hydrocracking catalyst, is generally 15～30%.Hydrocracking catalyst is for producing the middle oil type hydrocracking catalyst of intermediate oil.Acid cracking activity component generally is selected from molecular sieve and amorphous silicon aluminium, and often the molecular sieve type that uses has: Y zeolite, beta molecular sieve, type ZSM 5 molecular sieve, SAPO series molecular sieve, or the like.Simultaneously can also contain other refractory inorganic oxides in the hydrocracking catalyst, as the composite oxides of aluminum oxide, silicon oxide, titanium oxide and various elements or mixed oxide etc.
This technical scheme organically combines technologies such as the catalyzed conversion of desalted crude and catalytic wax oil hydrocracking, produces light-weight fuel oil to greatest extent from desalted crude, especially stop bracket gasoline and high hexadecane value diesel oil, thus the realization petroleum resources efficiently utilize.The present invention compared with prior art has following technique effect:
1, crude oil work flow provided by the present invention has been cancelled equipment such as process furnace in the conventional crude still-process and atmospheric and vacuum tower, can reduce facility investment and equipment anticorrosion expense.
2, pre-treatment crude oil is through catalyzed conversion among the present invention, and it is respond well that crude oil is removed carbon residue, and does not produce byproducts such as coke, pitch.
3, among the present invention crude oil through catalyzed conversion, good to the crude oil metal removal effect, demetallization per can near or reach more than 95%.Metal in the crude oil especially heavy metal is deposited on the catalyzer through fluidized catalytic conversion; And the present invention promotes medium with the light constituent instead of part water vapor in the crude oil, can make catalyst distribution even, and heavy metal at high temperature reacts with lighter hydrocarbons on the catalyzer, heavy metal loss part is active, obtain passivation to a certain degree, thereby suppressed the deleterious effect of heavy metal on the catalyzer, improved yield of light oil significantly, the slurry oil productive rate reduces significantly, thereby the petroleum resources utilising efficiency improves.
4, diesel yield increases significantly, and diesel cetane-number obviously improves.
5, under the situation that gasoline yield increases, gasoline octane rating improves significantly; And dry gas yied and coke reduce significantly.
6, the hydroeracking unit operational cycle is improved significantly.
7, catalyzer is more even because of particle, thereby partial temperature distribution is also more even in regenerative process, and the catalyst breakage tendency also correspondingly reduces.
8, catalyst consumption reduces, and the catalyst content in the slurry oil reduces.
Description of drawings
Accompanying drawing is the basic procedure synoptic diagram of the catalysis conversion method of crude production high-quality light Fuel provided by the invention.
Embodiment
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
Accompanying drawing is the basic procedure synoptic diagram of the catalysis conversion method of crude production high-quality light Fuel provided by the invention.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction, but therefore the present invention is not subjected to any restriction.
Embodiments of the present invention are to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
Its technical process is as shown in drawings:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, difficult cracking stock oil through pipeline 3 with bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction takes place in difficult cracking stock oil on the catalyzer of heat, and upwards accelerated motion.Easily cracking stock oil as low-density oil base crude oil through pipeline 5 with middle and upper part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction takes place in cracking stock oil on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Reaction product oil gas in the collection chamber 9 is through main oil gas piping 17, enter follow-up separation system 18, separating the propylene that obtains draws through pipeline 102, separating the propane that obtains draws through pipeline 103, carbon four hydrocarbon are drawn through pipeline 104, catalytic cracked dry gas is drawn through pipeline 101, catalytically cracked gasoline is drawn through pipeline 105, according to producing the needs boiling range is that 180～260 ℃ cut returns riser tube 2 through pipeline 106 and also can be used as catalytic diesel oil output, boiling range is that 260～330 ℃ diesel oil distillate can be drawn through pipeline 107, also can draw through pipeline 108 and enter hydrocracking unit 19 with catalytic wax oil (〉=330 ℃), isolating light constituent draws through pipeline 201, the hydrocracking light constituent can be used as light constituent and separates and obtain rocket engine fuel according to producing needs, high hexadecane value diesel oil etc. also can be used as heavy constituent and return the bottom of riser tube 2 reaction zone I through pipeline 202 with hydrogenation heavy oil.
The following examples will be further specified the present invention, but not thereby limiting the invention.In embodiment and the Comparative Examples employed stock oil be desalination, the pretreated crude oil that dewaters, its character is listed in table 1 respectively.
Employed catalytic converting catalyst preparation method is summarized as follows among the embodiment:
1), with 0.20kgNH
4Cl is dissolved in the 10kg water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 1.0kg (butt) crystallization product ZRP-1 zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 40gH
3PO
4(concentration 85%) and 45gFe (NO
3)
3Be dissolved in the 0.90kg water, dry with the filter cake hybrid infusion; Then handle at 550 ℃ of roasting temperatures and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2), configuration 200 liter silica concentrations are 155kg/m
3Water glass solution and 100 liter free acids be 148kg/m
3, Al
2O
3Content is 20kg/m
3Acidified aluminum sulfate solution, above-mentioned two kinds of solution enter flash mixer reaction simultaneously, obtain silicon sol.
The kaolin slurry that 45kg halloysite (Suzhou china clay company Industrial products, the heavy % of solid content 71.6) making beating is obtained with 25kg decationized Y sieve water; The above-mentioned silicon sol that has prepared is mixed with kaolin slurry, pulled an oar 1 hour.Add 5.5kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, Al again
2O
3Content is 33 heavy %) and the 45kg deionized water mix making beating 30 minutes, adding 2.5 liter concentration then is hydrochloric acid (acid/Al of 31 heavy %
2O
3Mol ratio is 0.2), its PH is transferred to 2～4, stir, under 60～70 ℃, leave standstill and obtained silicon oxide-kaolin-aluminum oxide mixed sols in aging 1 hour.
3), the MFI structure mesopore zeolite (butt is 2.0kg) and DASY zeolite (the Qilu Petrochemical company catalyst plant Industrial products of the phosphorous and iron that step 1) is prepared, lattice constant is 2.445～2.448nm, butt is 22.5kg) join step 2) in silicon oxide-kaolin-aluminum oxide mixed sols of obtaining, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+Be drying to obtain diameter and be 20～120 microns catalytic cracking catalyst sample, this catalyzer to consist of 2 heavy % phosphorous and MFI structure mesopore zeolite, 22 heavy %DASY zeolites, silica content iron be 32 heavy % pseudo-boehmites, 5 heavy % aluminium colloidal sol and surplus kaolin.
4) prepared catalyzer wears out through 800 ℃ and 100% water vapor, the aged catalyst property is listed in table 2, its code name is MDCO-1, again elutriation is carried out in the aging agent of part, remove fine particle and greater than 100 microns particle, obtain the catalyzer that coarse grain directly distributes, its code name is MDCO-2, and its character is listed in table 2.
Catalytic wax oil hydrocracking catalyst HCC, the preparation of its carrier is with 75g pseudo-boehmite (Shandong Aluminum Plant's Industrial products, Al
2O
3Content is 33 heavy %), 100gDASY zeolite (Qilu Petrochemical company catalyst plant Industrial products, lattice constant are 2.445-2.448nm, and butt is 22.5kg), 5gH
3PO
4(concentration 85%) and suitable amount of adhesive etc. mix, extruded moulding, 120 ℃ of dry 3hr, and 500 ℃ of roasting 4hr are ground into particle and promptly get particulate state DASY-Al
2O
3Carrier.Take by weighing ammonium metawolframate ((NH
4)
2W
4O
1318H
2O, chemical pure) and nickelous nitrate (Ni (NO
3)
218H
2O, chemical pure), water is made into 200mL solution.Solution is joined DASY-Al
2O
3In carrier 50 gram, at room temperature flooded 3 hours, used the ultrasonication steeping fluid 30 minutes in steeping process, cooling is filtered, and is put in the microwave oven dry about 15 minutes.Consisting of of this catalyzer: 30.0 heavy %WO
3, 3.1 heavy %NiO, 4.5 heavy %P
2O
5, 38 heavy % aluminum oxide and surplus SiO
2The character of wax oil hydrogenation cracking catalyst HCC is listed in table 2.
Embodiment 1
The present embodiment explanation adopts method provided by the invention to carry out catalyzed conversion and a large amount of high-quality gasoline situations of hydrocracking reaction production.
This embodiment tests according to the flow process of accompanying drawing, catalyzer is MDCO-2, stock oil A is directly as the easy cracking stock oil of catalytic cracking, on middle-scale device, test by riser reactor, easily cracking stock oil enters reaction zone I middle and upper part, and difficult cracking stock oil enters reaction zone I bottom.In reaction zone I bottom, difficult cracking stock oil is at 580 ℃ of temperature of reaction, weight hourly space velocity 240h
-1, the weight ratio 30 of catalytic cracking catalyst and difficult cracking stock oil, the weight ratio of water vapor and difficult cracking stock oil are to carry out cracking reaction under 0.20 condition; In reaction zone I middle and upper part, easily cracking stock oil is at 510 ℃ of temperature of reaction, weight hourly space velocity 90h
-1, the weight ratio 10 of catalytic cracking catalyst and easy cracking stock oil, water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil.At reaction zone II, reactant flow oil gas is at 495 ℃ of temperature of reaction, weight hourly space velocity 30h
-1, water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil.Reaction product oil gas separates at settling vessel with catalyzer to be generated, product cuts by boiling range in separation system, thereby to obtain propylene, gasoline, boiling range be 180～250 ℃ cut, diesel oil that boiling range is 250～330 ℃ and boiling range greater than 330 ℃ catalytic wax oil.Boiling range is easy oil circulation time catalytic convention design of cracking stock of cut conduct of 180～250 ℃.Catalytic wax oil is carried out hydrocracking again, adopts hydrocracking catalyst HCC, and catalyzer is at hydrogen dividing potential drop 12.0MPa, 385 ℃ of temperature of reaction, hydrogen to oil volume ratio 1300v/v, volume space velocity 1.0h
-1Reaction conditions under carry out hydrocracking, hydrogenation catalyst wax oil behind the hydrogenation cuts by boiling range, thereby obtain boiling range and be 180～250 ℃ rocket engine fuel, diesel oil that boiling range is 250～330 ℃ and greater than 330 ℃ products such as hydrogenation catalyst wax oil cut, hydrogenation catalyst wax oil cut greater than 330 ℃ loops back above-mentioned medium-sized catalytic convention design, enters riser reactor reaction zone I bottom as difficult cracking stock oil and carries out cracking again.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, stock oil A is through catalyzed conversion among the embodiment 1, and the catalytic wax oil productive rate is 31.58 heavy %, hydrogen richness 12.98 heavy %, and nickel and vanadium only are 0.2 μ gg
-1, carbon residue only is 0.44 heavy %; Stock oil A is through catalyzed conversion and hydrocracking, and gasoline yield is 41.35 heavy %, and its research octane number (RON) (RON) is up to 91.48, and motor-method octane number (MON) is 85; Diesel yield is 26.05 heavy %, and cetane value is 56; Jet fuel yield 17.74 heavy %; Lightweight oil total recovery 85.14 heavy %.Dry gas yield 1.01 heavy %, coke yield 2.28 heavy %.
Comparative Examples 1
Comparative Examples be with stock oil A directly as the raw material of catalytic cracking, the stock oil of test and testing sequence and method and embodiment 1 are identical, just the catalyzer that adopts changes catalyzer MDCO-1 into by the MDCO-2 of embodiment 1.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, with respect to embodiment 1, the catalytic wax oil productive rate of Comparative Examples 1 is low 0.98 heavy %, and its hydrogen richness low 0.12 heavy %, carbon residue exceeds 0.02 heavy %; And the lightweight oil total recovery is low, is 84.13 heavy %; Dry gas yied 1.25 heavy % and coke yield 2.98 heavy %, dry gas and coke yield have significantly to be increased.
The present embodiment explanation adopts method provided by the invention to carry out catalyzed conversion and the high-quality diesel oil situation of hydrocracking reaction mass production.
This embodiment is identical with the testing apparatus of embodiment 1, with MDCO-2 as catalyzer, stock oil B is directly as the difficult cracking stock oil of catalyzed conversion, on middle-scale device, test by riser reactor, difficult cracking stock oil enters the reaction of reaction zone I bottom, and easily cracking stock oil enters the reaction of reaction zone I middle and upper part.In reaction zone I bottom, difficult cracking stock oil is at 520 ℃ of temperature of reaction, weight hourly space velocity 300h
-1, the weight ratio 90 of catalytic converting catalyst and difficult cracking stock oil, the weight ratio of water vapor and difficult cracking stock oil are to carry out cracking reaction under 0.20 condition; In reaction zone I middle and upper part, easily cracking stock oil is at 480 ℃ of temperature of reaction, weight hourly space velocity 120h
-1, the weight ratio 30 of catalytic converting catalyst and easy cracking stock oil, water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil; In addition, replenish the steam stripped reclaimable catalyst of part from stripping stage and enter reaction zone II bottom, with temperature and the reaction weight hourly space velocity that reduces reaction zone II.At reaction zone II, oil gas is at 470 ℃ of temperature of reaction, weight hourly space velocity 20h
-1Water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil, oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain propylene, part carbon four hydrocarbon and gasoline, boiling range is the catalytic wax oil of 180～330 ℃ diesel oil and boiling range＞330 ℃.Catalytic wax oil is carried out hydrocracking again, at hydrogen dividing potential drop 15.0MPa, 420 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 0.5h
-1Reaction conditions under on catalyzer HCC, carry out hydrocracking, hydrogenation catalyst wax oil behind the hydrogenation cuts by boiling range, thereby obtain 150～240 ℃ rocket engine fuel, 240～330 ℃ diesel oil and greater than hydrogenation catalyst wax oil cut of 330 ℃ etc., hydrogenation catalyst wax oil cut greater than 260 ℃ loops back above-mentioned medium-sized catalytic convention design, enters catalytic convention design reaction zone I middle and upper part as easy cracking stock oil and carries out cracking again.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, stock oil B is through catalyzed conversion among the embodiment 2, and the catalytic wax oil productive rate is 40.23 heavy %, and nickel and vanadium only are 0.2 μ gg
-1, carbon residue only is 0.81 heavy %.After stock oil B catalyzed conversion and the catalytic wax oil hydrocracking, diesel yield is 46.23 heavy %, and cetane value is 54; Gasoline yield is 29.12 heavy %, and its research octane number (RON) (RON) is up to 90.52, and motor-method octane number (MON) is 84; Jet fuel yield 10.31 heavy %; Lightweight oil total recovery 85.66 heavy %; Dry gas yield 0.91 heavy %; Coke yield 2.79 heavy %.
Comparative Examples 2
This Comparative Examples be with stock oil B directly as the difficult cracking stock of catalytic cracking, the stock oil of test and testing sequence and method and embodiment 2 are identical, just the catalyzer that adopts changes catalyzer MDCO-1 into by the MDCO-2 of embodiment.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, with respect to embodiment 2, Comparative Examples 2 lightweight oil total recoverys are low, are 84.44 heavy %; Dry gas yield 1.13 heavy %; Coke yield 3.58 heavy %; Dry gas yied and coke yield have significantly to be increased.
Table 1
Table 2
| Catalyzer | MDCO-1 | MDCO-2 | HCC |
| The particle diameter type | Conventional particle diameter | The coarse grain footpath | |
| Chemical constitution, heavy % | |||
| Aluminum oxide | 8.5 | 8.4 | 44 |
| Sodium oxide | 0.29 | 0.27 | ＜0.1 |
| Ferric oxide | 1.0 | 1.0 | - |
| Nickel oxide | - | - | 5.6 |
| Tungsten oxide 99.999 | - | - | 24.3 |
| Rare earth | 0.9 | 1.0 | - |
| Apparent density, kilogram/rice 3 | 765 | 754 | 912 |
| Pore volume, milliliter/gram | 0.28 | 0.26 | 0.35 |
| Specific surface area, rice 2/ gram | 117 | 114 | 326 |
| Abrasion index, heavy % hour -1 | 1.4 | 1.3 | 0.52 |
| Size composition, heavy % | |||
| 0～40 micron | 22.4 | 9.1 | - |
| 40～80 microns | 54.0 | 76.4 | - |
| ＞80 microns | 23.6 | 14.5 | - |
Table 3
| Embodiment 1 | Comparative Examples 1 | |
| The stock oil numbering | A | A |
| Catalytic conversion unit | ||
| Catalyzer | MDCO-2 | MDCO-1 |
| The riser tube temperature out, ℃ | 490 | 490 |
| Riser reaction zone II | ||
| Temperature of reaction, ℃ | 500 | 500 |
| Weight hourly space velocity, h -1 | 20 | 20 |
| The weight ratio of water vapor/stock oil | 0.15 | 0.15 |
| Riser reaction zone I | ||
| Medial temperature, ℃ | 640/550 | 640/550 |
| Agent-oil ratio, m/m | 90/30 | 90/30 |
| Weight hourly space velocity, h -1 | 300/120 | 300/120 |
| The weight ratio of water vapor/stock oil | 0.20/0.15 | 0.20/0.15 |
| Catalytic wax oil | ||
| Yield, heavy % | 31.58 | 30.6 |
| Hydrogen richness, heavy % | 12.98 | 12.86 |
| Nickel+vanadium, μ gg -1 | 0.2 | 0.2 |
| Carbon residue, heavy % | 0.44 | 0.46 |
| The hydrocracking unit | ||
| Catalyzer | HCC | HCC |
| The hydrogen dividing potential drop, MPa | 18.0 | 18.0 |
| Temperature of reaction, ℃ | 450 | 450 |
| Hydrogen to oil volume ratio, v/v | 1500 | 1500 |
| Volume space velocity, h -1 | 0.5 | 0.5 |
| Product distributes, heavy % | ||
| Dry gas | 1.01 | 1.25 |
| Liquefied gas | 11.57 | 11.64 |
| Propylene and |
4.38 | 4.37 |
| Gasoline | 41.35 | 41.25 |
| Rocket engine fuel | 17.74 | 17.42 |
| Diesel oil | 26.05 | 25.46 |
| Coke | 2.28 | 2.98 |
| Gasoline property |
| Research octane number (RON) RON | 91.48 | 91.56 |
| Motor-method octane number MON | 85 | 85 |
| Diesel oil character | ||
| Density (20 ℃), gcm -3 | 0.8152 | 0.8146 |
| Zero pour, ℃ | -4 | -4 |
| Cetane value | 56 | 56 |
Table 4
| |
Comparative Examples 2 | |
| The stock oil numbering | B | B |
| Catalytic conversion unit | ||
| Catalyzer | MDCO-2 | MDCO-1 |
| The riser tube temperature out, ℃ | 475 | 475 |
| Riser reaction zone II | ||
| Temperature of reaction, ℃ | 480 | 480 |
| Weight hourly space velocity, h -1 | 30 | 30 |
| The weight ratio of water vapor/stock oil | 0.15 | 0.15 |
| Riser reaction zone I | ||
| Medial temperature, ℃ | 550/510 | 550/510 |
| Agent-oil ratio, m/m | 60/10 | 60/10 |
| Weight hourly space velocity, h -1 | 180/60 | 180/60 |
| The weight ratio of water vapor/stock oil | 0.20/0.15 | 0.20/0.15 |
| Catalytic wax oil | ||
| Yield, heavy % | 40.23 | 38.56 |
| Hydrogen richness, heavy % | 11.84 | 11.67 |
| Nickel+vanadium, μ gg -1 | 0.2 | 0.2 |
| Carbon residue, heavy % | 0.81 | 0.84 |
| The hydrocracking unit | ||
| Catalyzer | HCC | HCC |
| The hydrogen dividing potential drop, MPa | 10.0 | 10.0 |
| Temperature of reaction, ℃ | 350 | 350 |
| Hydrogen to oil volume ratio, v/v | 500 | 500 |
| Volume space velocity, h -1 | 1.5 | 1.5 |
| Product distributes, heavy % | ||
| Dry gas | 0.91 | 1.13 |
| Liquefied gas | 10.64 | 10.85 |
| Propylene and |
4.70 | 4.79 |
| Gasoline | 29.12 | 28.34 |
| Rocket engine fuel | 10.31 | 10.26 |
| Diesel oil | 46.23 | 45.84 |
| Coke | 2.79 | 3.58 |
| Gasoline property | ||
| Research octane number (RON) RON | 90.52 | 90.34 |
| Motor-method octane number MON | 84 | 83 |
| Diesel oil character | ||
| Density (20 ℃), gcm -3 | 0.8274 | 0.8268 |
| Zero pour, ℃ | -6 | -6 |
| Cetane value | 54 | 54 |
Claims (29)
1. the catalysis conversion method of crude production high-quality light Fuel, it is characterized in that catalyzer that crude oil directly distributes with the coarse grain that contains large pore zeolite in reactor contacts reacts, it is characterized in that temperature of reaction, the oil gas residence time, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, wherein said weight hourly space velocity is 25～100h
-1, described temperature of reaction is 420～600 ℃, described catalyzer and stock oil weight ratio are 1～30; Catalytic wax oil is further hydrocracking again.
2. according to the method for claim 1, it is characterized in that described crude oil is selected from or comprises in petroleum base crude oil and/or other mineral oil one or more mixture, wherein said petroleum base crude oil is selected from or comprises petroleum base crude oil, comprises in paraffinic crude, paraffin-intermediate base crude oil, centre-paraffinic crude, intermediate base crude oil, centre-naphthenic base crude, cycloalkanes-intermediate base crude oil, the naphthenic base crude one or more; Other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
3. according to the method for claim 2, it is characterized in that described petroleum base crude oil through desalination, dehydration pre-treatment, vanadium, nickel total value are not more than 30ppm in the crude oil after the processing, and its density is greater than 0.85gcm
-3
4. according to the method for claim 1, it is characterized in that described temperature of reaction is 450～550 ℃, weight hourly space velocity is 30～80h
-1, the weight ratio of catalyzer and stock oil is 2～25.
5. according to the method for claim 4, it is characterized in that described temperature of reaction is 460～520 ℃, weight hourly space velocity is 40～60h
-1, the weight ratio of catalyzer and stock oil is 3～14.
6. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is large pore zeolite and/or optional mesopore zeolite, and large pore zeolite accounts for 80～100 heavy % of zeolite gross weight.
7. according to the method for claim 6, it is characterized in that described large pore zeolite is selected from the Y series zeolite, comprise among Rare Earth Y, rare earth hydrogen Y, super steady Y, the high silicon Y one or more.
8. according to the method for claim 1, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios less than 40 microns particle.
9. according to the method for claim 8, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 5% for accounting for all particulate volume ratios less than 40 microns particle.
10. according to the method for claim 8 or 9, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 15% for accounting for all particulate volume ratios greater than 80 microns particle.
11. according to the method for claim 10, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios greater than 80 microns particle.
12. method according to claim 1, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
13. according to the method for claim 1, it is characterized in that in the described reactor, or described stock oil introduced in the reactor in the position of identical or different height more than.
14. method according to claim 1, it is characterized in that described method also comprises separates reaction product with catalyzer, catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises stop bracket gasoline, high hexadecane value diesel oil and catalytic wax oil.
15. according to the method for claim 1, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, the catalytic wax oil hydrogen richness is not less than 11.5 heavy %.
16. method according to claim 1, it is characterized in that the catalytic wax oil hydrocracking is under there is situation in hydrogen, contact with hydrocracking catalyst, at reaction pressure 4.0～16.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～10.0h
-1Reaction conditions react.
17. the catalysis conversion method of crude production high-quality light Fuel is characterized in that this method comprises the following steps:
(1) stock oil comprises difficult cracking stock oil and easy cracking stock oil, a position described stock oil is introduced in the reactor, or in the position of identical or different height more than described stock oil is introduced in the reactor;
(2) the catalyzer contact reacts that in reactor, directly distributes with the coarse grain that is rich in large pore zeolite earlier of difficult cracking stock oil, or be not later than easy cracking stock oil and react;
(3) temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil;
(4) reclaimable catalyst separates by cyclonic separator with reaction oil gas; Randomly, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration; Reaction oil gas obtains comprising the reaction product of stop bracket gasoline, high hexadecane value diesel oil, catalytic wax oil through separation;
(5) wherein catalytic wax oil obtains gasoline, high hexadecane value diesel oil and hydrogenation heavy oil through hydrocracking, and described hydrogenation heavy oil is oily or/and easy cracking stock oil turns back to step (1) or/and in the step (2) as difficult cracking stock.
18. according to the method for claim 17, it is characterized in that described difficult cracking stock grease separation from or comprise that density is greater than 0.90gcm
-3Crude oil with poor quality, slurry oil, diesel oil, gasoline in one or more mixture.
19. method according to claim 17, it is characterized in that described easy cracking stock grease separation from or comprise in petroleum base crude oil and/or other mineral oil one or more mixture, wherein said petroleum base crude oil is selected from or comprises petroleum base crude oil, comprises in paraffinic crude, paraffin-intermediate base crude oil, centre-paraffinic crude, intermediate base crude oil, centre-naphthenic base crude, cycloalkanes-intermediate base crude oil, the naphthenic base crude one or more; Other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
20., it is characterized in that described petroleum base crude oil density after desalination, processed is not more than 0.90gcm according to the method for claim 19
-3
21., it is characterized in that the reaction conditions of difficult cracking stock oil is: 520～650 ℃ of temperature of reaction, weight hourly space velocity 100～800h according to the method for claim 17
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is 0.05～1.0.
22., it is characterized in that the reaction conditions of easy cracking stock oil is: 420～550 ℃ of temperature of reaction, weight hourly space velocity 5～100h according to the method for claim 17
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1～30 of cracking stock oil, water vapor is 0.05～1.0 with the easy weight ratio of cracking stock oil.
23. according to the method for claim 17, the temperature of reaction that it is characterized in that easy cracking stock oil is 450～540 ℃, weight hourly space velocity is 10～90h
-1,, catalyzer and stock oil weight ratio are 3～14.
24. according to the method for claim 18, the temperature of reaction that it is characterized in that easy cracking stock oil is 460～520 ℃, weight hourly space velocity 30～50h
-1Be preferably 20～60h
-1
25. according to the method for claim 17, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, the catalytic wax oil hydrogen richness is not less than 11.5 heavy %.
26. according to the method for claim 17, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios less than 40 microns particle.
27. according to the method for claim 26, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 5% for accounting for all particulate volume ratios less than 40 microns particle.
28. according to the method for claim 26 or 27, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 15% for accounting for all particulate volume ratios greater than 80 microns particle.
29. according to the method for claim 28, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios greater than 80 microns particle.
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