CN101993726A - Method for preparing high-quality fuel oil from inferior crude oil - Google Patents
Method for preparing high-quality fuel oil from inferior crude oil Download PDFInfo
- Publication number
- CN101993726A CN101993726A CN2009101696688A CN200910169668A CN101993726A CN 101993726 A CN101993726 A CN 101993726A CN 2009101696688 A CN2009101696688 A CN 2009101696688A CN 200910169668 A CN200910169668 A CN 200910169668A CN 101993726 A CN101993726 A CN 101993726A
- Authority
- CN
- China
- Prior art keywords
- oil
- heavy
- reaction
- catalyst
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing high-quality fuel oil from inferior crude oil. The inferior crude oil enters first and second reaction zones of a catalytic conversion reactor in turn to contact a catalytic conversion catalyst and respectively perform primary reaction and secondary reaction, and after a reaction product and a spent catalyst are subjected to gas-solid separation, the spent catalyst is stripped and scorched in turn and is returned to the reactor for recycling; the reaction product is separated to obtain propylene, light fuel oil, catalyzed wax oil and other products, wherein the catalyzed wax oil enters a hydrocracking device and is separated to obtain products such as gasoline, an aviation fuel, diesel oil, hydrocracked tail oil and the like; and the hydrocracked tail oil is circulated to the first reaction zone of the catalytic conversion reactor and/or other catalytic conversion devices for further reaction to obtain a desired product, namely the light fuel oil, and a byproduct, namely the propylene. By the method, a diesel cetane number is improved.
Description
Technical field
The invention belongs to the catalyzed conversion combined method of hydrocarbon ils, more particularly, is the method that inferior feedstock oil is converted into a large amount of light-weight fuel oils, and diesel-fuel cetane number improves simultaneously.
Background technology
Former oil quality shows that mainly oil density becomes big along with the continuous increase of Oil extraction amount worse and worse, and viscosity uprises, and heavy metal content, sulphur content, nitrogen content, colloid and asphalt content and acid number uprise.At present, the price difference of crude oil with poor quality and high-quality crude is along with the shortage of petroleum resources is also increasing, cause cheap crude oil with poor quality exploitation and working method more and more to receive publicity, that is to say, improve the yield of lightweight oil from crude oil with poor quality as much as possible, this has brought great challenge for the processing technology of traditional crude oil.
Traditional heavy oil upgrading is divided into three class complete processings, and the first kind is a hydrogenation technique, mainly comprises hydrotreatment and hydrofining; Second class is a decarbonization process, mainly comprises solvent deasphalting, delayed coking and heavy oil fluid catalytic cracking; The 3rd class is an arene extracting process.Inferior heavy oil can improve hydrogen-carbon ratio by this three classes Technology, is lower boiling compound with the hydrocarbon conversion inferior.When inferior heavy oil adopts decarbonization process to handle, sulphur in the inferior heavy oil, nitrogen and heavy metal content and aromatic hydrocarbons, colloid and asphalt content are bigger to the influence of decarbonization process, the decarbonization process existing problems are that liquid product yield is low, and product property is poor, need to handle again.Resemble delay coking process, though the impurity removal percentage height, the green coke amount is more than 1.5 times of stock oil carbon residue, and how solid Jiao utilizes also is the problem that needs solution.Hydroprocessing technique can remedy the deficiency of decarbonization process, inferior heavy oil by hydrotreatment after, the liquid product yield height, product property is good, but that the hydrotreatment mode is often invested is bigger.And arene extracting process have the investment little, repay fast characteristics, not only can reach good effect aspect the heavy oil processing, and the by-product important chemical material is an aromatic hydrocarbons.
The Pros and Cons that exists separately at hydrogenation technique and decarbonization process, CN1448483A discloses a kind of hydrogenation technique and decarbonization process combined method, this method is that resid feed is at first relaxed thermally splitting, and then carry out solvent deasphalting with catalytically cracked oil, deasphalted oil is carried out hydrotreatment under the condition that hydrogenation catalyst and hydrogen exist.This method has not only reduced the severity of residual hydrogenation equipment, has prolonged the work-ing life of hydrogenation catalyst, and has improved the yield and the character of liquid product, but de-oiled asphalt is difficult to utilize.
CN1844325A discloses a kind of decarbonization process of heavy oil and method of hydrogenation technique organic assembling handled, this method is by solvent deasphalting technology and coking process combination treatment with inferior heavy oil, deasphalted oil after the processing and wax tailings are as the raw material of heavy-oil hydrogenation treatment unit, thereby improve the character of heavy-oil hydrogenation treatment unit charging, relax the operational condition of heavy-oil hydrogenation treatment unit, prolong the operational cycle of heavy-oil hydrogenation treatment unit, for the devices such as catalytic cracking in downstream provide fine stock oil.But this method technical process complexity, and liquid yield is low.
CN1382776A discloses the method for a kind of residual hydrocracking and catalytically cracking heavy oil, be that residual oil and slurry oil steam that thing, catalytic cracking heavily follow carburetion, optional distillate enters hydrotreater together, in the presence of hydrogen and hydrogenation catalyst, carry out hydrogenation reaction; After the generation oil of reaction gained steams petrol and diesel oil, hydrogenated residue enters catalytic cracking unit with optional vacuum gas oil, carry out cracking reaction in the presence of cracking catalyst, reaction gained heavy cycle oil enters residual hydrogenation equipment, and the distillation slurry oil obtains steaming thing and is back to hydrogenation unit.This method can be converted into light-end products with slurry oil and heavy cycle oil, has improved the yield of gasoline and diesel oil.Although heavy oil is by behind the hydroprocessing technique, catalytic cracking process can be produced more liquid product, and the foreign matter content of product is low, character makes moderate progress, but the density of working as heavy oil is big, and when viscosity height, heavy metal, colloid and asphalt content were high, the operational condition of hydrotreater was very harsh, the working pressure height, the temperature of reaction height, air speed is low, and on-stream time is short, the process cost height, and the one-time investment of device is also high.Residual hydrogenation equipment all changed constantly to the catalytically cracked stock character that provided latter stage from the operation initial stage, thereby operation produces adverse influence to catalytic cracking unit.The stock oil that the residual hydrogenation technology is processed is formed extremely complicated, stock oil not only contains sulphur, nitrogen and metal, and contain alkane, naphthenic hydrocarbon and aromatic hydrocarbons, and cracking reaction easily takes place in alkane molecule in the hydrotreatment process, generate the small molecules hydro carbons, even dry gas, thereby cause the heavy oil resource not reach effective utilization, simultaneously, when hydrogenated residue enters the catalytic cracking unit processing, still produce the heavy oil of 8～10 heavy %, cause the reduction of heavy oil efficiency of resource again, this heavy oil can return residual hydrogenation equipment, but this heavy oil and residual oil character differ bigger, and hydrogen richness is low, even through hydrotreatment, the character of this heavy oil is improved limited.
CN1746265A discloses a kind of catalyzed cracking processing technology of inferior oil material, this method obtains poor quality oil through catalytic cracking solar oil cut Returning catalyticing cracking device freshening, the heavy oil fraction that obtains carries out solvent extraction, the heavy aromatics that extracting goes out is as product, the Returning catalyticing cracking device freshening of raffinating oil.This method has solved the problem of heavy oil to a certain extent, but this method need be controlled final boiling point≤300 ℃ of solar oil cut, the final boiling point of heavy gas oil≤450 ℃, solar oil cut Returning catalyticing cracking device freshening wherein, heavy gas oil enters the aromatic extraction unit extracting, the Returning catalyticing cracking device of raffinating oil, though result's slurry oil amount decreases, but still higher relatively, and do not have diesel product, dry gas output is also bigger.
CN1766059A discloses the treatment process of a kind of inferior heavy oil or residual oil, this method at first enters the solvent extraction device with heavy oil or residual oil raw material, the deasphalted oil of gained enters the fixed bed hydrogenation treatment unit and carries out hydrotreatment, the gained hydrogenation tail oil enters catalytic cracking unit, wherein the part or all of slurry oil of gained enters the floating bed hydrogenation device with obtained deasphalted oil by solvent extraction, product obtains light ends and unconverted tail oil through separation, and wherein unconverted tail oil is circulated to the solvent extraction device.This method is organically with catalytic cracking process, extraction process and hydrogenation technique combination, and on heavy oil is handled certain effect arranged, but this method technical process complexity, and liquid yield is low.
Along with the development of oil recovery technique, a large amount of peracid, high calcium crude oil are exploited out.Calcium contamination owner in the crude oil will be non-porphyrin organic calcium compound, only be dissolved in petroleum fractions, conventional desalting method can not separate these organic calcium compounds from crude oil, when the acid number in the crude oil surpasses 0.5mgKOH/g, will cause equipment corrosion, conventional atmospheric and vacuum distillation unit equipment is difficult to processing highly acid crude oil.For this reason, CN1827744A discloses a kind of method of processing crude oil with high acid value, this method is to make pretreated total acid value inject fluid catalytic cracking reactor greater than the crude oil of 0.5mgKOH/g after preheating to contact with catalyzer, and under the catalytic cracking reaction condition, react, oil gas behind the separating reaction and catalyzer, reaction oil gas is delivered to subsequent separation system, and reacted catalyzer recycles after stripping, regeneration.This method has that industrial applicibility is strong, running cost is low and advantage such as deacidification effect is good, but dry gas and coke yield are higher, cause the benefit of utilizing of petroleum resources to reduce.
For a long time, those of ordinary skills think that the transformation efficiency of heavy oil fluid catalytic cracking is high more good more.But the contriver through thinking creatively and repeatedly experiment find that the transformation efficiency of heavy oil fluid catalytic cracking is not high more good more, when transformation efficiency high to a certain degree, the increase of purpose product seldom, the productive rate of dry gas and coke but increases considerably.In order efficiently to utilize the inferior heavy oil resource, satisfy the demand of growing light-weight fuel oil, being necessary to develop a kind of is a large amount of lightweights and the catalysis conversion method of clean fuel oil with the inferior heavy oil feedstock conversion.Above-mentioned prior art still exists not enough to alkane molecule cracking reaction design, causing is increasing under the productivity of propylene situation, dry gas yied increases considerably, simultaneously, prior art is underused the gasoline potential content in gasoline octane rating and the diesel oil, cause productivity of propylene on the low side, there are room for improvement in gasoline yield and quality simultaneously.In order to satisfy the growing low-carbon alkene industrial chemicals and the demand of motor spirit, PCT/CN2009/000272 discloses a kind of method of producing light-weight fuel oil and propylene from inferior feedstock oil, first and second reaction zone that inferior feedstock oil enters catalytic conversion reactor successively contacts with catalytic converting catalyst primary first-order equation, secondary reaction takes place respectively, reaction product and reclaimable catalyst after gas solid separation, reclaimable catalyst successively through stripping, burn again after Returning reactor recycle; Reaction product obtains propylene, gasoline, catalytic wax oil and other product through separation, and wherein said catalytic wax oil enters aromatic extraction unit, separates to obtain extracting oil out and raffinating oil; Described first reaction zone that is circulated to catalytic conversion reactor of raffinating oil obtains purpose product propylene and gasoline or/and other catalytic convention design is further reacted.Inferior feedstock oil is after relaxing catalyzed conversion in this method, and resulting catalytic wax oil is extracted out in the oil and is rich in double ring arene through the aromatic hydrocarbons extracting, is good industrial chemicals; Raffinate oil and be rich in alkane and naphthenic hydrocarbon, be fit to very much carry out catalyzed conversion, realized that petroleum resources efficiently utilize.This method can reduce dry gas yied and coke yield significantly, but this method diesel cetane-number is relatively low.
In order efficiently to utilize the inferior heavy oil resource, satisfy the demand of growing light-weight fuel oil, being necessary to develop a kind of is a large amount of lightweights and the catalysis conversion method of clean fuel oil with the inferior heavy oil feedstock conversion.
Summary of the invention
Technical problem to be solved by this invention is that the inferior heavy oil catalytic material is converted into a large amount of cleaning light-weight fuel oils, and diesel-fuel cetane number improves simultaneously.
Method of the present invention comprises the following steps:
(1), first reaction zone that the inferior feedstock oil of preheating enters catalytic conversion reactor contacts the generation cracking reaction with the catalytic converting catalyst of heat, oil gas that generates and used catalyst optional with second reaction zone that enters catalytic conversion reactor after lightweight material oil and/or cold shock medium mix, carry out cracking reaction, hydrogen transfer reactions and isomerization reaction, the reclaimable catalyst of reaction product and reaction back band charcoal is after gas solid separation, reaction product enters separation system and is separated into dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil, reclaimable catalyst is transported to revivifier and carries out coke burning regeneration behind the water vapor stripping, the regenerated catalyst Returning reactor of heat recycles; Wherein said first reaction zone and the second reaction zone reaction conditions are enough to make reaction to obtain comprising the catalytic wax oil product that accounts for the heavy % in stock oil 12 heavy %～60 heavy % preferred 20 heavy %～40;
(2), described catalytic wax oil enters hydroeracking unit and further handles the product that obtains comprising petroleum naphtha, rocket engine fuel, diesel oil and hydrogenation tail oil;
(3), described hydrocracking tail oil is circulated to one or more equipment in first reaction zone, other catalytic convention design, steam cracking device, hydroeracking unit of step (1) catalytic conversion reactor as its raw material.
Technical scheme of the present invention is so concrete enforcement:
The inferior feedstock oil of preheating enters catalytic conversion reactor under the castering action of water vapor first reaction zone contacts with the regeneration catalyzing conversion catalyst of heat, be 510 ℃～650 ℃ in temperature of reaction and be preferably 520 ℃～600 ℃, reaction times be preferably 0.1 second in 0.05 second～1.0 seconds～0.5 second, the weight ratio of catalyzer and stock oil (hereinafter to be referred as agent-oil ratio) is 3～15: 1 is preferably 4～12: 1, the weight ratio of water vapor and stock oil (hereinafter to be referred as water-oil ratio) is 0.03～0.3: 1 is preferably 0.05～0.2: 1, pressure is that the macromole cracking reaction takes place under the condition of 130kPa～450kPa, removes metal in the inferior feedstock oil, sulphur, nitrogen, at least a impurity in the naphthenic acid;
Oil gas that generates and used catalyst or with second reaction zone that enters catalytic conversion reactor after lightweight material oil that injects and/or cold shock medium mix, being 420 ℃～550 ℃ in temperature of reaction, to be preferably 460 ℃～530 ℃, reaction times be to be preferably 2 seconds in 1.5 seconds～20 seconds～to carry out cracking reaction, hydrogen transfer reactions and isomerization reaction under 10 seconds the condition; Reaction product isolated obtains dry gas, liquefied gas (comprising propylene, propane and C4 hydrocarbon), gasoline, diesel oil and catalytic wax oil, and wherein propane, C4 hydrocarbon, diesel oil also can be used as the lightweight material oil of described second reaction zone;
Described catalytic wax oil is separately or with after diesel oil and/or other heavy oil mix, enter hydroeracking unit, obtain products such as petroleum naphtha, rocket engine fuel, diesel oil and hydrocracking tail oil, hydrocracking tail oil is circulated to one or more equipment in first reaction zone, other catalytic convention design, steam cracking device, hydroeracking unit of step (1) catalytic conversion reactor as its raw material.
Other catalytic convention design is conventional catalytic cracking unit and various improved device thereof, and preferably the description that device is more detailed is referring to patent CN1232069A and CN1232070A.
Described inferior feedstock oil is heavy petroleum hydrocarbon and/or other mineral oil, and wherein heavy petroleum hydrocarbon is selected from one or more the mixture of arbitrary proportion in vacuum residuum (VR), inferior long residuum (AR), hydrogenated residue inferior, coker gas oil, deasphalted oil, crude oil with high acid value, the high metal crude oil; Other mineral oil is one or more in liquefied coal coil, tar sand oil, the shale oil.
Described inferior raw material oil properties satisfies a kind of in the following index at least:
Density is 900～1000 kilograms/meter
3, be preferably 930～960 kilograms/meter
3Carbon residue is that 4～15 heavy % are preferably 4～12 heavy %; Metal content is 15～600ppm, is preferably 15～100ppm; Acid number is 0.5～20mgKOH/g, is preferably 0.5～10.0mgKOH/g.
Described lightweight material grease separation one or more in liquefied gas, gasoline, diesel oil, described liquefied gas is from the liquefied gas of present method gained and/or the liquefied gas of other method gained; Described gasoline is selected from the gasoline of present method gained gasoline and/or other method gained; Described diesel oil is the diesel oil that is selected from present method gained diesel oil and/or other method gained.
Described catalytic wax oil is that the boiling range produced of this device or external device such as conventional catalytic cracking is greater than 200 ℃, more preferably greater than 300 ℃ catalytic wax oil.
The reactive system of hydroeracking unit generally includes refining reaction device and cracking case, be fixed-bed reactor, the refining reaction device loads hydrotreating catalyst usually, this hydrotreating catalyst be load on unformed aluminum oxide or/and the group vib on the silica-alumina supports or/and VIII family non-precious metal catalyst; Hydrocracking catalyst is to load on group vib on the y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst.Wherein said group vib base metal is a molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, the iron.
The processing condition of described hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.Hydrogen-oil ratio among the present invention all refers to the volume ratio of hydrogen and catalytic wax oil.
Described hydrocracking tail oil is that this device or this device and external device such as conventional catalytic cracking institute production catalytic wax oil are resultant through hydrocracking.
Described cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst, refrigerative half regenerated catalyst, reclaimable catalyst and the live catalyst, and wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; 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.
Described gasoline or diesel oil boiling range are adjusted by actual needs, are not limited only to whole process gasoline or diesel oil.Described catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: the heavy % in zeolite 1 heavy %～50, the heavy % in the heavy % in inorganic oxide 5 heavy %～99, clay 0 heavy %～70.Its mesolite is as active ingredient, be selected from mesopore zeolite and/or optional large pore zeolite, mesopore zeolite accounts for the heavy % in 0 heavy %～100 of zeolite gross weight, the heavy % in preferred 20 heavy %～80, large pore zeolite accounts for the heavy % in 0 heavy %～100 of zeolite gross weight, the heavy % in preferred 20 heavy %～80.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.Large pore zeolite is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y constitute.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Clay is selected from kaolin and/or halloysite as matrix (being carrier).
Described catalyzer also can be the employed useless equilibrium catalyst of conventional catalytic cracking unit.
Two reaction zones of catalytic cracking in this method can be suitable for the catalyzer of same type, also can be suitable for dissimilar catalyzer, and dissimilar catalyzer can be different catalyzer of granular size and/or the different catalyzer of apparent bulk density.Active ingredient also can be selected dissimilar zeolites respectively for use on the different catalyzer of catalyzer that granular size is different and/or apparent bulk density.The catalyzer of particulate catalyzer and/or the height apparent bulk density of varying in size can enter different reaction zones respectively, for example, the oarse-grained catalyzer that contains ultrastable Y enters first reaction zone, increase cracking reaction, the short grained catalyzer that contains rare earth Y type zeolite enters second reaction zone, increase hydrogen transfer reactions, the catalyzer that granular size is different is regenerated at same stripper stripping and same revivifier, isolate macrobead and catalyst particle then, catalyst particle enters second reaction zone through cooling.The catalyzer that granular size is different is to demarcate between 30～40 microns, and the catalyzer that apparent bulk density is different is with 0.6～0.7g/cm
3Between the boundary.
The reactor that this method catalytic cracking unit is suitable for can be selected from the equal diameter riser tube, etc. the linear speed riser tube, one of become in diameter riser tube or the fluidized-bed, also can be the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.Preferably select for use and become the compound reactor that diameter riser reactor or equal diameter riser tube and fluidized-bed constitute.
Described fluidized-bed reactor be selected from riser tube, etc. fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, one or both series combinations of downstriker transfer limes of linear speed.Riser tube can be conventional isodiametric riser tube, also can be the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1 meter per second～2 meter per seconds, and the gas speed of riser tube is 2 meter per seconds～30 meter per seconds (disregarding catalyzer).
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.
This technical scheme organically combines technologies such as catalytic cracking, hydrocracking and conventional catalytic cracking, produce propylene and light-weight fuel oil to greatest extent from inferior raw material, especially stop bracket gasoline improves diesel-fuel cetane number, thereby realizes that petroleum resources efficiently utilize.The present invention compared with prior art has following unforeseeable technique effect:
1, the catalytic wax oil that obtains through catalytic cracking earlier of inferior feedstock oil is then through hydrocracking, thereby the feedstock property of hydroeracking unit is improved significantly;
2, because the stock oil character that hydroeracking unit is processed improves, the hydroeracking unit operational cycle is improved significantly;
3, because the character of hydrocracking tail oil is improved, and yield of light oil increases significantly, the slurry oil productive rate reduces significantly, has realized that petroleum resources efficiently utilize.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is a process flow diagram of the present invention.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, regeneration catalyzing conversion catalyst from pipeline 16 moves upward at the pre-castering action lower edge riser tube that promotes medium, stock oil inferior 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 inferior raw material on the catalyzer of heat, and moves upward.Lightweight material oil through pipeline 5 with bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, cracking reaction takes place in lightweight material oil on the lower catalyzer of coke content, and move upward, 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, and 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 2 through inclined tube 16.
Oil gas in the collection chamber 9 enters follow-up separation system 18 through main oil gas piping 17, separates the propylene that obtains and draws through pipeline 19, separates the propane that obtains and draws through pipeline 28; And carbon four hydrocarbon are drawn through pipeline 20, also can return riser tube 2; The catalytic pyrolysis dry gas is drawn through pipeline 21; Catalytic cracking gasoline is drawn through pipeline 27, and preferred boiling range is drawn conduct cracking stock Returning reactor again less than 65～110 ℃ of gasoline fractions through pipeline 22; Diesel oil distillate is drawn through pipeline 29, also the diesel oil lighting end can be returned riser tube 2, also the heavy gas oil cut can be drawn with catalytic wax oil and enter the hydrocracking unit; Catalytic wax oil is drawn out to hydrocracking unit 24 through pipeline 23, and isolated hydrocracking product further separates through pipeline 25, and hydrocracking tail oil is sent into this reactor or/and voluminous gasoline device 27 through pipeline 26.The oil gas that fecund gasoline device generates can enter fractionating system 18 or/and enter other fractionating system and separate through gas pipeline 28.Wherein each cut boiling range is regulated according to refinery's actual needs.
The following examples will give further instruction to present method, but therefore not limit present method.
Used raw material is vacuum residuum, long residuum inferior, hydrogenated residue inferior and acid-containing raw oil among the embodiment, and its character is as shown in table 1.
Catalytic cracking catalyst GZ-1 preparation method used among the embodiment is summarized as follows:
1), with 20gNH
4Cl is dissolved in the 1000g water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 100g (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 4.0gH
3PO
4(concentration 85%) and 4.5gFe (NO
3)
3Be dissolved in the 90g 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), use 250kg decationized Y sieve water with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) again, its PH is transferred to 2～4 with hydrochloric acid, stir, left standstill under 60～70 ℃ aging 1 hour, keeping PH is 2～4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical company catalyst plant product, Al
2O
3Content is 21.7m%), stirred 40 minutes, obtain mixed serum.
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 the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+, being drying to obtain the catalytic cracking catalyst sample, consist of 2 heavy % MFI structure mesopore zeolite, 18 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 7 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Conventional catalytic cracking catalyst is respectively MLC-500 and CGP-1, and its character is listed in table 2.
The used Hydrobon catalyst and the trade names of hydrocracking catalyst are respectively RN-2 and RT-1 among the embodiment, produce by Sinopec catalyzer branch office Chang Ling catalyst plant.
This embodiment implements by accompanying drawing, vacuum residuum feed oil A is as the raw material of catalytic cracking, on the middle-scale device of riser reactor, test, inferior raw material enters reaction zone I bottom, contact with catalyzer GZ-1 and react, in reaction zone I bottom, raw material inferior is at 595 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalyzer and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.05 condition; At reaction zone II, oil gas is at 500 ℃ of temperature of reaction, weight hourly space velocity 30h
-1The weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05 condition, oil gas separates at settling vessel with the catalyzer of band charcoal, product cuts by boiling range in separation system, thereby obtain dry gas, liquefied gas (comprises propylene, propane and C4 hydrocarbon, down with), gasoline, diesel oil and cut point be greater than 320 ℃ catalytic wax oil, catalytic wax oil is sent into the hydrocracking unit then, the reactive system of this hydroeracking unit comprises refining reaction device and two reactors of cracking case, at hydrogen dividing potential drop 12.0/11.5MPa, 375/371 ℃ of temperature of reaction, volume space velocity 0.90/1.1h
-1Reaction conditions under carry out hydrocracked, treated, the hydrocracking tail oil after the hydrocracking enters another set of kitty cracker same as described above, adopts catalyzer MLC-500, at reaction zone I, 595 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalyzer and raw material, at reaction zone II, 500 ℃ of temperature of reaction, weight hourly space velocity 20h
-1, the weight ratio 6 of catalytic cracking catalyst and raw material is isolated dry gas, liquefied gas, gasoline, and diesel oil and catalytic wax oil, catalytic wax oil are returned the hydrocracked, treated device.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, total liquid yield is up to 89.60 heavy %, and wherein gasoline yield is up to 36.58 heavy %, productivity of propylene is up to 4.66 heavy %, and diesel yield is up to 25.18 heavy %, and the rocket engine fuel productive rate is up to 13.85 heavy %, and dry gas yied only is 3.30 heavy %, and the slurry oil productive rate only is 0.6 heavy %.The octane value of gasoline (RON) is 90.5, and diesel-fuel cetane number is 31.0.
Comparative Examples 1
This Comparative Examples is directly as the raw material of catalytic cracking with vacuum residuum feed A, on medium-sized riser reactor device, test, in 500 ℃ of temperature of reaction, reaction times is 2.5 seconds, the weight ratio 6 of catalyzer and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.05 condition; Oil gas separates at settling vessel with the catalyzer of band charcoal, and product cuts by boiling range in separation system, thereby obtains dry gas, liquefied gas, gasoline, diesel oil, slurry oil.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, total liquid yield only is 77.44 heavy %, and wherein gasoline yield only is 43.76 heavy %, and productivity of propylene only is 4.21 heavy %, and dry gas yied weighs % up to 3.49, and the slurry oil productive rate is up to 9.18 heavy %.Compare with embodiment 1, the Comparative Examples total liquid yield reduces significantly, causes the reduction of petroleum resources utilising efficiency.The octane value of gasoline (RON) only is 90.5, and diesel-fuel cetane number only is 24.5.
This embodiment tests according to the flow process of accompanying drawing, high-acid crude oil raw material B is as the raw material of catalytic cracking, on the middle-scale device of riser reactor, test, inferior raw material enters reaction zone I bottom, contact with catalyzer GZ-1 and react, in reaction zone I bottom, raw material inferior is at 595 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalyzer and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.05 condition; At reaction zone II, oil gas is at 500 ℃ of temperature of reaction, weight hourly space velocity 30h
-1The weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05 condition, oil gas separates at settling vessel with the catalyzer of band charcoal, product cuts by boiling range in separation system, thereby obtain dry gas, comprise liquefied gas, the gasoline of propylene, diesel oil and cut point are greater than 310 ℃ catalytic wax oil, catalytic wax oil is sent into the hydrocracking unit then, the reactive system of this hydroeracking unit comprises refining reaction device and two reactors of cracking case, at hydrogen dividing potential drop 12.0/11.5MPa, 375/371 ℃ of temperature of reaction, volume space velocity 0.90/1.1h
-1Reaction conditions under carry out hydrocracked, treated, the hydrocracking tail oil after the hydrocracking enters the kitty cracker of another set of routine, adopts catalyzer CGP-1, at reaction zone I, 595 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalytic cracking catalyst and raw material, the weight ratio 0.10 of water vapor/raw material, at reaction zone II, 500 ℃ of temperature of reaction, weight hourly space velocity 20h
-1, the weight ratio 6 of catalytic cracking catalyst and raw material is isolated dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil, and catalytic wax oil is returned hydrotreater.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, total liquid yield is up to 88.02 heavy %, and wherein gasoline yield is up to 32.90 heavy %, and productivity of propylene is up to 6.81 heavy %, and diesel yield is up to 23.94 heavy %, and the rocket engine fuel productive rate is up to 11.396 heavy %, and dry gas yied only is 3.70 heavy %.The octane value of gasoline (RON) is 90.1, and diesel-fuel cetane number is 31.5.
Comparative Examples 2
This Comparative Examples is directly as the raw material of catalytic cracking with high-acid crude oil raw material B, on medium-sized riser reactor device, test, adopt catalyzer CGP-1, in 500 ℃ of temperature of reaction, reaction times is 2.5 seconds, the weight ratio 6 of catalyzer and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.10 condition; Oil gas separates at settling vessel with the catalyzer of band charcoal, and product cuts by boiling range in separation system, thereby obtains dry gas, liquefied gas, gasoline, diesel oil, slurry oil.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, total liquid yield only is 77.29 heavy %, and wherein gasoline yield only is 35.43 heavy %, and productivity of propylene only is 6.52 heavy %, and dry gas yied weighs % up to 5.51, and the slurry oil productive rate is up to 6.22 heavy %.Compare with embodiment 3, the Comparative Examples total liquid yield reduces significantly, causes the reduction of petroleum resources utilising efficiency.The octane value of gasoline (RON) only is 89.5, and diesel-fuel cetane number only is 25.3.
Table 1
| The stock oil title | Vacuum residuum | High-acid crude oil |
| The stock oil code name | A | B |
| Density (20 ℃), kilogram/rice 3 | 920.9 | 902.2 |
| Kinematic viscosity, millimeter 2/ second | ||
| 80℃ | / | 52.5 |
| 100℃ | 114.4 | / |
| Carbon residue, heavy % | 8.2 | 7.89 |
| Condensation point, |
25 | / |
| Acid number, mgKOH/g | / | 3.62 |
| Total nitrogen, heavy % | 0.33 | 0.36 |
| Sulphur, heavy % | 0.21 | 0.14 |
| Carbon, heavy % | 86.91 | 86.33 |
| Hydrogen, heavy % | 12.55 | 12.66 |
| Metal content, ppm | ||
| Nickel | 8.8 | 61.0 |
| Vanadium | 0.1 | 3.4 |
| Iron | 1.8 | 13.2 |
| Copper | ＜0.1 | / |
| Sodium | 3.0 | 43 |
| Calcium | 4.4 |
Table 2
Table 3
| |
Comparative Examples 1 | |
| The stock oil numbering | A | A |
| Reactor | The series connection riser tube | Riser tube |
| Catalytic cracking unit | ||
| Operational condition | ||
| Catalyzer | GZ-1 | / |
| The riser tube temperature out, ℃ | 500 | / |
| Reaction zone I/II temperature, ℃ | 595/500 | / |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/30 | / |
| Agent- |
6 | / |
| Water-oil ratio | 0.05 | / |
| The hydrotreatment unit | ||
| The hydrogen dividing potential drop, MPa | 12.0/11.5 | / |
| Temperature, ℃ | 375/371 | / |
| Volume space velocity, h -1 | 0.90/1.10 | / |
| Hydrogen-oil ratio, v/v | 705/900 | / |
| Conventional catalytic cracking unit | ||
| Catalyzer | MLC-500 | MLC-500 |
| The riser tube temperature out, ℃ | / | 500 |
| Reaction zone I/II temperature, ℃ | 595/500 | / |
| Reaction zone I/II weight hourly space velocity or reaction times, h -1Or second | 100/20 | 2.5 second |
| Agent- |
6 | 6 |
| Water-oil ratio | 0.05 | 0.05 |
| Product distributes, heavy % | ||
| Dry gas | 3.30 | 3.49 |
| Liquefied gas | 13.99 | 13.50 |
| Propylene | 4.66 | 4.21 |
| Gasoline | 36.58 | 43.76 |
| Rocket engine fuel | 13.85 | / |
| Diesel oil | 25.18 | 20.18 |
| Slurry oil | 0.60 | 9.18 |
| Coke | 7.22 | 9.89 |
| Add up to | 100.72 | 100.0 |
| Total liquid yield, heavy % | 89.60 | 77.44 |
| Gasoline RON | 90.5 | 90.0 |
| Diesel cetane-number | 31.0 | 24.5 |
Table 4
| |
Comparative Examples 2 | |
| The stock oil numbering | B | B |
| Reactor | The series connection riser tube | Riser tube |
| Catalytic cracking unit | ||
| Operational condition | ||
| Catalyzer | GZ-1 | / |
| The riser tube temperature out, ℃ | 500 | / |
| Reaction zone I/II temperature, ℃ | 595/500 | / |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/30 | / |
| Agent- |
6 | / |
| Water-oil ratio | 0.05 | / |
| The hydrotreatment unit | ||
| The hydrogen dividing potential drop, MPa | 12.0/11.5 | / |
| Temperature, ℃ | 375/371 | / |
| Volume space velocity, h -1 | 0.90/1.10 | / |
| Hydrogen-oil ratio, v/v | 705/900 | / |
| Conventional catalytic cracking unit | ||
| Catalyzer | CGP-1 | CGP-1 |
| The riser tube temperature out, ℃ | 500 | 500 |
| Reaction zone I/II temperature, ℃ | 595/500 | |
| Reaction zone I/II weight hourly space velocity or reaction times, h -1Or second | 100/20h -1 | 2.5 second |
| Agent- |
6 | 6 |
| Water-oil ratio | 0.10 | 0.10 |
| Product distributes, heavy % | ||
| Dry gas | 3.70 | 5.51 |
| Liquefied gas | 19.85 | 19.10 |
| Propylene | 6.81 | 6.52 |
| Gasoline | 32.90 | 35.43 |
| Rocket engine fuel | 11.36 | / |
| Diesel oil | 23.94 | 22.76 |
| Slurry oil | / | 6.22 |
| Coke | 8.18 | 10.16 |
| Oxygenatedchemicals | 0.75 | 0.82 |
| Add up to | 100.66 | 100.00 |
| Total liquid yield, heavy % | 88.02 | 77.29 |
| Gasoline RON | 90.1 | 89.5 |
| Diesel cetane-number | 31.5 | 25.3 |
Above-mentioned all reference are all incorporated this paper for all useful purposes into through quoting.
Although show and described concrete manifestation some embodiment of the present invention, but those skilled in the art it is evident that, can under the situation that does not deviate from the spirit and scope that constitute principle of the present invention, make various variations and modification, and this is not limited to the illustrational specific form of this paper.
Claims (21)
1. produce the method for high-grade fuel oil from inferior feedstock oil for one kind, it is characterized in that this method comprises the following steps:
(1), first reaction zone that the inferior feedstock oil of preheating enters catalytic conversion reactor contacts the generation cracking reaction with the catalytic converting catalyst of heat, oil gas that generates and used catalyst optional with second reaction zone that enters catalytic conversion reactor after lightweight material oil and/or cold shock medium mix, carry out cracking reaction, hydrogen transfer reactions and isomerization reaction, the reclaimable catalyst of reaction product and reaction back band charcoal is after gas solid separation, reaction product enters separation system and is separated into dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil, reclaimable catalyst is transported to revivifier and carries out coke burning regeneration behind the water vapor stripping, the regenerated catalyst Returning reactor of heat recycles; Wherein said first reaction zone and the second reaction zone reaction conditions are enough to make reaction to obtain comprising the catalytic wax oil product that accounts for the heavy % in stock oil 12 heavy %～60;
(2), described catalytic wax oil enters hydroeracking unit and further handles the product that obtains comprising petroleum naphtha, rocket engine fuel, diesel oil and hydrogenation tail oil;
(3), described hydrocracking tail oil is circulated to one or more equipment in first reaction zone, other catalytic convention design, steam cracking device, hydroeracking unit of step (1) catalytic conversion reactor as its raw material.
2. according to the method for claim 1, it is characterized in that described inferior feedstock oil is heavy petroleum hydrocarbon and/or other mineral oil, wherein heavy petroleum hydrocarbon is selected from one or more the mixture of arbitrary proportion in vacuum residuum, inferior long residuum, hydrogenated residue inferior, coker gas oil, deasphalted oil, crude oil with high acid value, the high metal crude oil; Other mineral oil is one or more in liquefied coal coil, tar sand oil, the shale oil.
3. according to the method for claim 1 or 2, it is characterized in that described inferior raw material oil properties satisfies a kind of in the following index at least: density is 900～1000 kilograms/meter
3, carbon residue is 4～15 heavy %, and metal content is 15～600ppm, and acid number is 0.5～20mgKOH/g.
4. according to the method for claim 3, it is characterized in that described inferior raw material oil properties satisfies at least a in the following index: density is 930～960 kilograms/meter
3, carbon residue is 4～12 heavy %, metal content is that 15～100ppm and acid number are 0.5～10mgKOH/g.
5. according to the method for claim 1, it is characterized in that described first reaction zone and the second reaction zone reaction conditions are to be enough to make reaction to obtain comprising the catalytic wax oil product that accounts for the heavy % in stock oil 20 heavy %～40.
6. according to the method for claim 1, it is characterized in that described lightweight material grease separation one or more kinds in liquefied gas, gasoline, diesel oil.
7. according to the method for claim 1, it is characterized in that described cold shock medium is the mixture that is selected from the arbitrary proportion of one or more kinds in cold shock agent, refrigerative regenerated catalyst, refrigerative half regenerated catalyst, reclaimable catalyst and the live catalyst, wherein the cold shock agent is the mixture that is selected from the arbitrary proportion of one or more kinds in liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively.
8. according to the method for claim 1, it is characterized in that described catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % in zeolite 1 heavy %～50, the heavy % in the heavy % in inorganic oxide 5 heavy %～99, clay 0 heavy %～70, its mesolite is as active ingredient, be mesopore zeolite and/or optional large pore zeolite, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the mixture of one or more kinds in this group zeolite that is made of Rare Earth Y, rare earth hydrogen Y, super steady Y and high silicon Y.
9. according to the method for claim 1, it is characterized in that the condition of first reaction zone comprises: temperature of reaction is that 510 ℃～650 ℃, weight hourly space velocity are 10～200h
-1, catalyzer and stock oil weight ratio be 3～15: 1, the weight ratio of water vapor and stock oil is 0.03～0.3: 1, pressure is 130kPa～450kPa.
10. according to the method for claim 9, it is characterized in that the condition of first reaction zone comprises: temperature of reaction is that 520 ℃～600 ℃, weight hourly space velocity are 15～150h
-1, catalyzer and stock oil weight ratio be 4～12: 1, the weight ratio of water vapor and stock oil is 0.05～0.2: 1, pressure is 130kPa～450kPa.
11. according to the method for claim 1, it is characterized in that the condition of second reaction zone comprises: temperature of reaction is that 420 ℃～550 ℃, weight hourly space velocity are 5～150h
-1
12. according to the method for claim 11, it is characterized in that the condition of second reaction zone comprises: temperature of reaction is that 460 ℃～530 ℃, weight hourly space velocity are 15～80h
-1
13. according to the method for claim 1, it is characterized in that propane and C4 hydrocarbon in the described liquefied gas, and at least a in the diesel oil enters described second reaction zone as lightweight material oil.
14. method according to claim 1, it is characterized in that hydrocracking catalyst is to load on group vib on the y-type zeolite molecular sieve or/and VIII family non-precious metal catalyst, wherein said group vib base metal is a molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, the iron.
15. according to the method for claim 1, it is characterized in that the processing condition of hydrocracking are: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, volume space velocity 0.1～20h
-1, hydrogen-oil ratio 300～2000v/v.
16. according to the method for claim 1, it is characterized in that described catalytic wax oil cutting temperature is not less than 250 ℃, hydrogen richness is not less than 10.5 heavy %.
17. want 16 method, it is characterized in that the cutting temperature of described catalytic wax oil is not less than 330 ℃ that hydrogen richness is not less than 10.8 heavy % according to right.
18., it is characterized in that described mesopore zeolite accounts for the heavy % in 0 heavy % of zeolite gross weight～50 according to the method for claim 8.
19., it is characterized in that described mesopore zeolite accounts for the heavy % in 0 heavy % of zeolite gross weight～20 according to the method for claim 18.
20. method according to claim 1, it is characterized in that described reactor be selected from riser tube, etc. the combination of one or more kinds in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with two or more the combination 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.
21., it is characterized in that described riser tube is the reducing riser reactor according to the method for claim 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101696688A CN101993726B (en) | 2009-08-31 | 2009-08-31 | Method for preparing high-quality fuel oil from inferior crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101696688A CN101993726B (en) | 2009-08-31 | 2009-08-31 | Method for preparing high-quality fuel oil from inferior crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101993726A true CN101993726A (en) | 2011-03-30 |
| CN101993726B CN101993726B (en) | 2013-11-27 |
Family
ID=43784492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101696688A Active CN101993726B (en) | 2009-08-31 | 2009-08-31 | Method for preparing high-quality fuel oil from inferior crude oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101993726B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059988A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method for petroleum hydrocarbon |
| CN103059995A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Effective catalytic conversion method of petroleum hydrocarbon |
| CN103059996A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method of petroleum hydrocarbon |
| CN103059989A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Effective catalytic conversion method for petroleum hydrocarbon |
| CN103059990A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Efficient catalytic conversion method for petroleum hydrocarbon |
| CN103059993A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method of petroleum hydrocarbon |
| CN103627426A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Method for improving gasoline yield of catalytic cracking technology and device thereof |
| CN109705901A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN109705910A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN112708461A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing more propylene and low-sulfur fuel oil components |
| CN112877097A (en) * | 2019-11-29 | 2021-06-01 | 中石油克拉玛依石化有限责任公司 | Processing method and device for poor-quality catalytic cracking raw material |
| CN115595176A (en) * | 2022-08-24 | 2023-01-13 | 宁波中金石化有限公司（Cn） | Method for reducing solid-phase product content in pyrolysis catalytic product of residual oil-hydrocracking tail oil by using modified iron sand microspheres |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
| CN1160746A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Gasoline octane number-raising catalytic conversion method |
| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
-
2009
- 2009-08-31 CN CN2009101696688A patent/CN101993726B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
| CN1160746A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Gasoline octane number-raising catalytic conversion method |
| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059989B (en) * | 2011-10-20 | 2015-03-18 | 中国石油化工股份有限公司 | Effective catalytic conversion method for petroleum hydrocarbon |
| CN103059990A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Efficient catalytic conversion method for petroleum hydrocarbon |
| CN103059988A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method for petroleum hydrocarbon |
| CN103059989A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Effective catalytic conversion method for petroleum hydrocarbon |
| CN103059988B (en) * | 2011-10-20 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic conversion method for petroleum hydrocarbon |
| CN103059993A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method of petroleum hydrocarbon |
| CN103059995A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Effective catalytic conversion method of petroleum hydrocarbon |
| CN103059996B (en) * | 2011-10-20 | 2015-01-14 | 中国石油化工股份有限公司 | Catalytic conversion method of petroleum hydrocarbon |
| CN103059995B (en) * | 2011-10-20 | 2015-03-18 | 中国石油化工股份有限公司 | Effective catalytic conversion method of petroleum hydrocarbon |
| CN103059990B (en) * | 2011-10-20 | 2015-03-18 | 中国石油化工股份有限公司 | Efficient catalytic conversion method for petroleum hydrocarbon |
| CN103059996A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Catalytic conversion method of petroleum hydrocarbon |
| CN103627426A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Method for improving gasoline yield of catalytic cracking technology and device thereof |
| CN109705901A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN109705910A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN109705910B (en) * | 2017-10-26 | 2021-01-08 | 中国石油化工股份有限公司 | Method and system for hydrocracking heavy raw oil |
| CN109705901B (en) * | 2017-10-26 | 2021-01-08 | 中国石油化工股份有限公司 | Method and system for hydrocracking heavy raw oil |
| CN112708461A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing more propylene and low-sulfur fuel oil components |
| CN112708461B (en) * | 2019-10-24 | 2022-06-24 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and low-sulfur fuel oil components |
| CN112877097A (en) * | 2019-11-29 | 2021-06-01 | 中石油克拉玛依石化有限责任公司 | Processing method and device for poor-quality catalytic cracking raw material |
| CN115595176A (en) * | 2022-08-24 | 2023-01-13 | 宁波中金石化有限公司（Cn） | Method for reducing solid-phase product content in pyrolysis catalytic product of residual oil-hydrocracking tail oil by using modified iron sand microspheres |
| CN115595176B (en) * | 2022-08-24 | 2023-12-29 | 宁波中金石化有限公司 | Method for reducing content of solid-phase product in residual oil-hydrocracking tail oil pyrolysis catalytic product by utilizing modified iron sand microspheres |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101993726B (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101942340B (en) | Method for preparing light fuel oil and propylene from inferior raw material oil | |
| CN101531924B (en) | Method for preparing light fuel oil and propylene from poor-quality raw oil | |
| CN101993726B (en) | Method for preparing high-quality fuel oil from inferior crude oil | |
| CN101531558B (en) | Catalytic conversion method for preparing propylene and aromatic hydrocarbons | |
| CN101531923B (en) | Catalytic conversion method for preparing propylene and high-octane gasoline | |
| CN101724430B (en) | Method for preparing light-weight fuel oil and propylene from inferior raw oil | |
| CN101747928B (en) | Catalytic conversion method for preparing lower olefins and aromatics | |
| CN101987972B (en) | Method for processing inferior crude oil through combined processes | |
| CN101760227B (en) | Catalytic conversion method for preparing propylene and high octane gasoline | |
| CN101063047B (en) | Method of dense raw material hydrotreatment-catalytic cracking for improving propylene productivity | |
| CN102021031B (en) | Method for preparing superior fuel oil from inferior crude oil | |
| CN101899323B (en) | Catalytic conversion method for converting low-quality heavy oil into light clean fuel oil | |
| CN102344831A (en) | Petroleum hydrocarbon catalytic conversion method | |
| CN101760228A (en) | Catalytic conversion method for preparing propylene and high octane gasoline | |
| CN101724431B (en) | Catalytic conversion method for preparing light fuel oil and propylene | |
| CN101935266B (en) | Catalytic conversion method for preparing propylene and high-octane value gasoline | |
| CN102021030B (en) | Catalytic conversion method | |
| CN102031147B (en) | Catalytic conversion method for producing diesel and propylene in high yield | |
| CN109722307A (en) | The method and system of processing of heavy oil | |
| CN101993328B (en) | Catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield | |
| CN102465036B (en) | Shale oil processing method for producing propylene | |
| CN102031138A (en) | Catalytic conversion method for productive diesel and propylene | |
| CN102079995B (en) | Catalytic conversion method for producing high-quality light fuel by using crude oil | |
| CN102134509B (en) | Catalytic conversion method for preparing propylene and high-octane gasoline with crude oil | |
| CN102108308B (en) | Catalyst conversion method for producing high-octane gasoline by using crude oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |