CN101531924A - Method for preparing light fuel oil and propylene from poor-quality raw oil - Google Patents
Method for preparing light fuel oil and propylene from poor-quality raw oil Download PDFInfo
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Abstract
A method for preparing light fuel oil and propylene from poor-quality raw oil comprises the following steps: the poor-quality raw oil sequentially enters a first reaction zone and a second reaction zone of a catalytic conversion reactor so as to be contacted with a catalytic conversion catalyst to generate first reaction and second reaction respectively, and after gas-solid separation is implemented to reaction products and spent catalyst, the spent catalyst returns to the reactor for recycling after steam stripping and burning; the reaction products are separated to obtain propylene, gasoline, heavy oil and other products, wherein the heavy oil is contacted with hydrogen and a hydrotreating catalyst for reaction, the obtained hydrogenated heavy oil circulates to the first reaction zone of the catalytic conversion reactor or/and other catalytic conversion devices for further reaction to obtain the target products of the propylene and the gasoline. The characteristic of the heavy oil obtained by hydrotreating after the mild catalytic conversion of the poor-quality raw oil is significantly improved, thereby significantly increasing light oil, reducing dry gas, reducing the yield of oil slurry and realizing the high-efficient utilization of petroleum resources.
Description
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils, more particularly, is the method that inferior raw material is converted into a large amount of light-weight fuel oil and propylene by the combination of hydrocarbon oil catalytic cracking and hydroprocessing technique process.
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 two class complete processings, and wherein a class is a hydrogenation technique, mainly comprises hydrotreatment and hydrofining; Another kind of is decarbonization process, mainly comprises heavy oil fluid catalytic cracking, delayed coking and solvent deasphalting.Inferior heavy oil can improve hydrogen-carbon ratio by this two 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.
The Pros and Cons that exists separately at hydrogenation technique and decarbonization process, CN1169920C 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.
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 oil sulphur content, 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.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of, inferior heavy oil is converted into the especially catalysis conversion method of stop bracket gasoline of light-weight fuel oil by catalytic conversion process and hydroprocessing technique organic assembling.
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 cracking reaction of generation macromole with the regeneration catalyzing conversion catalyst of heat, 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, under the certain reaction environment, 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, propylene, propane, the C4 hydrocarbon, gasoline, diesel oil and heavy 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;
(2), described heavy oil enters hydrotreater, contacts with hydrogen, hydrotreating catalyst and reacts, the generation oil behind the hydrogenation is removed the lighter hydrocarbons molecule through stripping and is obtained hydrogenation heavy oil;
(3), described hydrogenation heavy oil is circulated to first reaction zone of step (1) catalytic conversion reactor or/and the further reaction of other catalytic convention design obtains purpose product propylene and gasoline.
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 that 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 that 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, propylene, propane, C4 hydrocarbon, gasoline, diesel oil and heavy oil, and wherein propane, C4 hydrocarbon, diesel oil also can be used as the lightweight material oil of described second reaction zone;
Described heavy oil is separately or with after diesel oil and/or other heavy oil mix, enter hydrotreating reactor, under there is situation in hydrogen, contact with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, generation oil behind the hydrogenation is removed the lighter hydrocarbons molecule through stripping, and first reaction zone that the hydrogenation heavy oil behind the stripping is circulated to catalytic conversion reactor obtains purpose product propylene and gasoline or/and other catalytic convention design is further reacted.
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 4～10 heavy %; Metal content is 15～600g/g, is preferably 15～100g/g; 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 heavy 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 ℃ heavy oil.
Described hydrogenation heavy oil be the boiling range produced of this device or this device and external device such as conventional catalytic cracking greater than 200 ℃, resultant more preferably greater than 300 ℃ heavy oil through hydrotreatment.Hydrogenation heavy oil is as the stock oil of conventional catalytic cracking unit.
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 catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: the heavy % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of 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 % of 0 heavy %-100 of zeolite gross weight, the heavy % of preferred 20 heavy %-80, large pore zeolite accounts for the heavy % of 0 heavy %-100 of zeolite gross weight, the heavy % of 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.
Described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier, preferred hydrotreating catalyst is that one or more group VIII metals, 12～39 one or more group vib metals of heavy % and surplus aluminum oxide and/or the amorphous silicon aluminium carrier by 0～10 heavy % additive, 1～9 heavy % constitutes, and wherein said additive is selected from non-metallic element and metallic elements such as fluorine, phosphorus, titanium, platinum.Described group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
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 second, and the gas speed of riser tube is 2 meter per seconds-30 meter per second (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.
The reactor that this method hydrotreatment unit is suitable for is fixed-bed reactor.
This technical scheme organically combines technologies such as catalytic cracking, hydrotreatment and conventional catalytic cracking, produces propylene and light-weight fuel oil to greatest extent from inferior raw material, stop bracket gasoline especially, thus realize that petroleum resources efficiently utilize.The present invention compared with prior art has following unforeseeable technique effect:
1, inferior heavy oil is first through catalytic cracking, hydrotreatment then, thus the feedstock property of hydrotreater improves significantly;
2, inferior heavy oil is after catalytic cracking, and resulting heavy oil contains more polycyoalkane and less long chain alkane, thereby hydrogenation heavy oil character can obtain improving more significantly, and the lighter hydrocarbons molecule that hydrotreatment generated, and especially dry gas also reduces significantly;
3, the stock oil character of processing owing to hydrotreater improves, thereby the hydrotreater operational cycle is improved significantly;
4, hydrotreater is more stable to the catalytically cracked stock character that provided latter stage from the operation initial stage, thereby helps the catalytic cracking unit operation;
5, hydrogenation heavy oil character is improved, thereby yield of light oil increases significantly, and the slurry oil productive rate reduces significantly, has realized that petroleum resources efficiently utilize.
Description of drawings
Fig. 1 is the process flow diagram of embodiments of the present invention one.
Fig. 2 is the process flow diagram of embodiments of the present invention two.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is the process flow diagram of embodiments of the present invention one, and in this embodiment, hydrogenation heavy oil is circulated to first reaction zone of the described catalytic conversion reactor of present method.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regeneration catalyzing conversion catalyst of pipeline 16 in the accelerated motion that makes progress of 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 upwards accelerated motion.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 on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, 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 through inclined tube 16.
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 20, separating the propane that obtains draws through pipeline 21, and the C4 hydrocarbon is drawn through pipeline 22, propane and C4 hydrocarbon can be used as part lightweight material oil content is not circulated to above-mentioned catalytic convention design through pipeline 30 and 29 riser tube 2 reaction zone II, catalytic cracked dry gas is drawn through pipeline 19, gasoline fraction is drawn through pipeline 23, diesel oil distillate is drawn through pipeline 24, diesel oil distillate can be used as part lightweight material oil is circulated to above-mentioned catalytic convention design through pipeline 28 riser tube 2 reaction zone II, heavy oil fraction is transported to hydrotreatment unit 24 through pipeline 25, isolated light constituent is drawn through pipeline 26, hydrogenation heavy oil is circulated to the riser tube 2 reaction zone I of above-mentioned catalytic convention design through pipeline 27, further produces low alkene stop bracket gasoline, propylene and diesel oil.
Fig. 2 is the process flow diagram of embodiments of the present invention two, and in this embodiment, hydrogenation heavy oil is circulated to other catalytic convention design.The technical process of this embodiment and embodiment one basic identical, unique difference is that hydrogenation heavy oil enters another set of catalytic convention design 31 through pipeline 27, further produces low alkene stop bracket gasoline, propylene (not shown).
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, maintenance 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 22.5kg) 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 2.0kg) 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 15 heavy % MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Hydrotreating catalyst preparation method used among the embodiment is summarized as follows: 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 in alumina supporter 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 and surplus aluminum oxide.
Conventional catalytic cracking catalyst is respectively MLC-500 and CGP-1, and its character is listed in table 2.
This embodiment tests according to the flow process of Fig. 1, 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 600 ℃ 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 mixes the back at 500 ℃ of temperature of reaction, weight hourly space velocity 30h with round-robin propane and C4 hydrocarbon, diesel oil
-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 for the treatment of 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 greater than 330 ℃ heavy oil, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation loops back above-mentioned kitty cracker, adopts catalyzer MLC-500, at reaction zone I, 600 ℃ 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, diesel oil and heavy oil, and heavy oil returns hydrotreater.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, total liquid yield is up to 88.39 heavy %, and wherein gasoline yield is up to 51.75 heavy %, and productivity of propylene is up to 5.05 heavy %, and dry gas yied only is 2.62 heavy %, and the slurry oil productive rate only is 1.10 heavy %.
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 for the treatment of charcoal, and product cuts by boiling range in separation system, thereby obtains dry gas, liquefied gas, gasoline, heavy 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.
This embodiment tests according to the flow process of Fig. 2, hydrogenated residue raw material C inferior 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 600 ℃ 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 mixes the back at 500 ℃ of temperature of reaction, weight hourly space velocity 30h with cooling regenerated catalyst as the cold shock medium
-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 for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain dry gas, liquefied gas and propylene, gasoline, diesel oil and greater than 330 ℃ heavy oil, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation enters the kitty cracker of another set of routine, adopts catalyzer CGP-1, at reaction zone I, 600 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalytic cracking catalyst 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, diesel oil and heavy oil, and heavy oil returns hydrotreater.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, total liquid yield is up to 87.49 heavy %, and wherein gasoline yield is up to 41.35 heavy %, and productivity of propylene is up to 8.04 heavy %, and dry gas yied only is 2.68 heavy %, and the slurry oil productive rate only is 1.30 heavy %.
Comparative Examples 2
This Comparative Examples is directly as the raw material of catalytic cracking with hydrogenated residue raw material C inferior, 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 for the treatment of charcoal, and product cuts by boiling range in separation system, thereby obtains dry gas, liquefied gas, gasoline, heavy 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 33.04 heavy %, and productivity of propylene only is 7.06 heavy %, and dry gas yied weighs % up to 3.63, and the slurry oil productive rate is up to 9.77 heavy %.Compare with embodiment 2, the Comparative Examples total liquid yield reduces significantly, causes the reduction of petroleum resources utilising efficiency.
Embodiment 3
This embodiment tests according to the flow process of Fig. 2, high-acid crude oil raw material E 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 600 ℃ 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 for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain dry gas, liquefied gas and propylene, gasoline, diesel oil and greater than 330 ℃ heavy oil, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation enters the kitty cracker of another set of routine, adopts catalyzer CGP-1, at reaction zone I, 600 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 6 of catalytic cracking catalyst 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, diesel oil and heavy oil, and heavy oil returns hydrotreater.Operational condition and product distribute and list in table 5.
As can be seen from Table 5, total liquid yield is up to 87.51 heavy %, and wherein gasoline yield is up to 40.17 heavy %, and productivity of propylene is up to 7.57 heavy %, and dry gas yied only is 3.21 heavy %.
Comparative Examples 3
This Comparative Examples is directly as the raw material of catalytic cracking with high-acid crude oil raw material E, 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 for the treatment of charcoal, and product cuts by boiling range in separation system, thereby obtains dry gas, liquefied gas, gasoline, heavy oil.Operational condition and product distribute and list in table 5.
As can be seen from Table 5, 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.
This embodiment tests according to the flow process of Fig. 2, long residuum B and crude oil with high acid value D are respectively 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 600 ℃ 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 for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain dry gas, liquefied gas and propylene, gasoline, diesel oil and greater than 330 ℃ heavy oil, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 2000v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation enters conventional kitty cracker, adopts catalyzer MLC-500, at reaction zone I, 600 ℃ 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 catalyzer and raw material is isolated dry gas, liquefied gas, gasoline, diesel oil and heavy oil, and heavy oil returns hydrotreater.Operational condition and product distribute and list in table 6.
As can be seen from Table 6, total liquid yield is respectively up to 86.02 heavy % and 85.44 heavy %, wherein gasoline yield is respectively up to 41.63 heavy % and 45.76 heavy %, productivity of propylene is respectively up to 5.05 heavy % and 4.21 heavy %, and dry gas yied only is respectively 2.89 heavy % and 3.03 heavy %, and the slurry oil productive rate only is respectively 2.30 heavy % and 2.18 heavy %.
Table 1
| The stock oil title | Vacuum residuum | Vacuum residuum | Hydrogenated residue inferior | High-acid crude oil | High-acid crude oil |
| The stock oil code name | A | B | C | D | E |
| Density (20 ℃), kilogram/rice 3 | 920.9 | 980 | 942.7 | 932.5 | 902.2 |
| Kinematic viscosity, millimeter 2/ second | |||||
| 80℃ | / | / | 137.7 | 156.45 | 52.5 |
| 100℃ | 114.4 | / | 62.78 | / | / |
| Carbon residue, heavy % | 8.2 | 13.95 | 8.0 | 6.7 | 7.89 |
| Condensation point, |
25 | / | / | / | / |
| Acid number, mgKOH/g | / | / | / | 12.52 | 3.62 |
| Total nitrogen, heavy % | 0.33 | 1.02 | / | / | 0.36 |
| Sulphur, heavy % | 0.21 | 1.39 | 0.24 | / | 0.14 |
| Carbon, heavy % | 86.91 | 85.35 | 87.82 | / | 86.33 |
| Hydrogen, heavy % | 12.55 | 11.14 | 12.07 | / | 12.66 |
| Metal content, ppm | |||||
| Nickel | 8.8 | 64.0 | 7.4 | 19.3 | 61.0 |
| Vanadium | 0.1 | 5.3 | 8.2 | 1.1 | 3.4 |
| Iron | 1.8 | / | 11.1 | / | 13.2 |
| Copper | <0.1 | / | / | / | / |
| Sodium | 3.0 | / | 1.2 | / | 43 |
| Calcium | 7.4 | 557 | 4.4 | ||
| Boiling range, ℃ | |||||
| Initial boiling point | 415 | / | 287 | / | / |
| 10％ | 545 | / | 394 | / | / |
| 30％ | / | / | 473 | / | / |
| 50％ | / | / | 558 | / | / |
| 70％ | / | / | / | / | / |
| 90％ | / | / | / | / | / |
| Final boiling point | / | / | / | / | / |
Table 2
| The catalyzer numbering | MLC-500 | GZ-1 | CGP-1 |
| Zeolite type | Large pore zeolite | Mesopore and large pore zeolite | Mesopore and large pore zeolite |
| Chemical constitution, heavy % | |||
| Aluminum oxide | 50.2 | 40.0 | 56.3 |
| Sodium oxide | 0.321 | 0.29 | 0.19 |
| Ferric oxide | / | 1.1 | / |
| Rare earth | 2.5 | 3.2 | |
| Apparent density, kg/m 3 | 700 | 750 | 630 |
| Pore volume, milliliter/gram | 0.38 | 0.40 | 0.36 |
| Specific surface area, rice 2/ gram | 229 | 196 | 221 |
| Abrasion index is when weighing % -1 | 1.9 | 1.5 | 1.7 |
| Size composition, heavy % | |||
| 0～40 micron | 17.3 | 20.2 | 13.1 |
| 40～80 microns | 49.3 | 50.1 | 41.8 |
| 80 microns | 33.4 | 29.7 | 45.1 |
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, ℃ | 600/500 | / |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/25 | / |
| The weight ratio of water vapor/raw material | 0.05 | / |
| The hydrotreatment unit | ||
| Temperature, ℃ | 350 | / |
| Volume space velocity, h -1 | 1.5 | / |
| Hydrogen to oil volume ratio, v/v | 1500 | / |
| Conventional catalytic cracking unit | ||
| Catalyzer | / | MLC-500 |
| The riser tube temperature out, ℃ | / | 520 |
| Reaction zone I/II temperature, ℃ | / | / |
| Reaction zone I/II weight hourly space velocity, h -1 | / | 2.5 second |
| The weight ratio of water vapor/raw material | / | 0.05 |
| Product distributes, heavy % | ||
| Dry gas | 2.62 | 3.49 |
| Liquefied gas | 15.62 | 13.50 |
| Propylene | 5.05 | 4.21 |
| Gasoline | 51.75 | 43.76 |
| Diesel oil | 21.02 | 20.18 |
| Slurry oil | 1.10 | 9.18 |
| Coke | 7.89 | 9.89 |
| Add up to | 100 | 100.0 |
| Total liquid yield, heavy % | 88.39 | 77.44 |
| Gasoline octane rating | ||
| RON | 91.2 | 91.0 |
| MON | 80.0 | 78.1 |
Table 4
| |
Comparative Examples 2 | |
| The stock oil numbering | C | C |
| 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, ℃ | 600/500 | / |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/25 | / |
| The weight ratio of water vapor/raw material | 0.05 | / |
| The hydrotreatment unit | ||
| Temperature, ℃ | 350 | / |
| Volume space velocity, h -1 | 1.5 | / |
| Hydrogen to oil volume ratio, v/v | 1500 | / |
| Conventional catalytic cracking unit | ||
| Catalyzer | CGP-1 | CGP-1 |
| The riser tube temperature out, ℃ | 500 | 500 |
| Reaction zone I/II temperature, ℃ | 600/500 | |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/20 | 2.5 second |
| The weight ratio of water vapor/raw material | 0.10 | 0.10 |
| Product distributes, heavy % | ||
| Dry gas | 2.68 | 3.63 |
| Liquefied gas | 22.32 | 20.17 |
| Propylene | 8.04 | 7.06 |
| Gasoline | 41.35 | 33.04 |
| Diesel oil | 23.82 | 24.08 |
| Slurry oil | 1.30 | 9.77 |
| Coke | 8.53 | 9.31 |
| Add up to | 100 | 100.0 |
| Total liquid yield, heavy % | 87.49 | 77.29 |
| Gasoline octane rating | ||
| RON | 94.5 | 94.0 |
| MON | 84.0 | 83.1 |
Table 5
| Embodiment 3 | Comparative Examples 3 | |
| The stock oil numbering | E | E |
| 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, ℃ | 600/500 | / |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/25 | / |
| The weight ratio of water vapor/raw material | 0.05 | / |
| The hydrotreatment unit | ||
| Temperature, ℃ | 350 | / |
| Volume space velocity, h -1 | 1.5 | / |
| Hydrogen to oil volume ratio, v/v | 1500 | / |
| Conventional catalytic cracking unit | ||
| Catalyzer | CGP-1 | CGP-1 |
| The riser tube temperature out, ℃ | 500 | 500 |
| Reaction zone I/II temperature, ℃ | 600/500 | |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/20 | 2.5 second |
| The weight ratio of water vapor/raw material | 0.10 | 0.10 |
| Product distributes, heavy % | ||
| Dry gas | 3.21 | 5.51 |
| Liquefied gas | 21.62 | 19.10 |
| Propylene | 7.57 | 6.52 |
| Gasoline | 40.17 | 35.43 |
| Diesel oil | 25.72 | 22.76 |
| Slurry oil | / | 6.22 |
| Coke | 8.50 | 10.16 |
| Oxygenatedchemicals | 0.78 | 0.82 |
| Add up to | 100.00 | 100.00 |
| Total liquid yield, heavy % | 87.51 | 77.29 |
| Gasoline octane rating | ||
| RON | 91.0 | 90.0 |
| MON | 80.0 | 78.8 |
Table 6
| |
|
|
| The stock oil numbering | B | D |
| Reactor | The series connection riser tube | The series connection riser tube |
| Catalytic cracking unit | ||
| Operational condition | ||
| Catalyzer | GZ-1 | GZ-1 |
| The riser tube temperature out, ℃ | 500 | 500 |
| Reaction zone I/II temperature, ℃ | 600/500 | 600/500 |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/25 | 100/25 |
| The weight ratio of water vapor/raw material | 0.05 | 0.05 |
| The hydrotreatment unit | ||
| Temperature, ℃ | 350 | 350 |
| Volume space velocity, h -1 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio, v/v | 2000 | 2000 |
| Conventional catalytic cracking unit | ||
| Catalyzer | MLC-500 | MLC-500 |
| The riser tube temperature out, ℃ | 500 | 500 |
| Reaction zone I/II temperature, ℃ | 600/500 | 600/500 |
| Reaction zone I/II weight hourly space velocity, h -1 | 100/20 | 100/20 |
| The weight ratio of water vapor/raw material | 0.05 | 0.05 |
| Product distributes, heavy % | ||
| Dry gas | 2.89 | 3.03 |
| Liquefied gas | 13.23 | 13.50 |
| Propylene | 5.05 | 4.21 |
| Gasoline | 41.63 | 45.76 |
| Diesel oil | 31.16 | 26.18 |
| Slurry oil | 2.30 | 2.18 |
| Coke | 8.89 | 9.03 |
| Add up to | 100 | 99.68 |
| Total liquid yield, heavy % | 86.02 | 85.44 |
| Gasoline octane rating | ||
| RON | 96.0 | 92.6 |
| MON | 84.0 | 81.1 |
Claims (13)
1, a kind ofly produces the method for light-weight fuel oil and propylene, it is characterized in that this method comprises the following steps: from inferior feedstock oil
(1), first reaction zone that the inferior feedstock oil of preheating enters catalytic conversion reactor contacts the cracking reaction of generation macromole with the regeneration catalyzing conversion catalyst of heat, 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, under the certain reaction environment, 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, propylene, propane, the C4 hydrocarbon, gasoline, diesel oil and heavy 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;
(2), described heavy oil enters hydrotreater, contacts with hydrogen, hydrotreating catalyst and reacts, the generation oil behind the hydrogenation is removed the lighter hydrocarbons molecule through stripping and is obtained hydrogenation heavy oil;
(3), described hydrogenation heavy oil is circulated to first reaction zone of step (1) catalytic conversion reactor or/and the further reaction of other catalytic convention design obtains purpose product propylene and gasoline.
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 15～600g/g, and acid number is 0.5～20mgKOH/g.
4,, it is characterized in that described lightweight material grease separation one or more in liquefied gas, gasoline, diesel oil according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that 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, 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.
6, method according to 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 % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of 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 by Rare Earth Y, rare earth hydrogen Y, the super steady Y that different methods obtains, the mixture of one or more in this group zeolite that high silicon Y constitutes.
7, according to the method for claim 1, it is characterized in that the condition of first reaction zone: temperature of reaction is that 510 ℃～650 ℃, reaction times are that the weight ratio of 0.05 second～1.0 seconds, catalyzer and stock oil is that the weight ratio of 3～15:1, water vapor and stock oil is that 0.03～0.3:1, pressure are 130kPa～450kPa.
8, according to the method for claim 7, it is characterized in that the condition of first reaction zone: temperature of reaction is that 520 ℃～600 ℃, reaction times are that the weight ratio of 0.1 second～0.5 second, catalyzer and stock oil is that the weight ratio of 4～12:1, water vapor and stock oil is that 0.05～0.2:1, pressure are 130kPa～450kPa.
9, according to the method for claim 1, it is characterized in that the condition of second reaction zone: temperature of reaction is that 420 ℃～550 ℃, reaction times are 1.5 seconds～20 seconds.
10, according to the method for claim 9, it is characterized in that the condition of second reaction zone: temperature of reaction is that 460 ℃～530 ℃, reaction times are 2 seconds～10 seconds.
11,, it is characterized in that at least a described second reaction zone of lightweight material oil that can be used as in described propane, C4 hydrocarbon, the diesel oil according to the method for claim 1.
12,, it is characterized in that described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier according to the method for claim 1.
13, according to the method for claim 1, it is characterized in that the condition of described hydrotreatment: hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1
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| CN 200810101854 CN101531924B (en) | 2008-03-13 | 2008-03-13 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
| US12/921,436 US8597500B2 (en) | 2008-03-13 | 2009-03-13 | Process for converting inferior feedstock to high quality fuel oil |
| JP2010550019A JP5879038B2 (en) | 2008-03-13 | 2009-03-13 | Method for obtaining light fuel from low quality feedstock |
| RU2010133616/04A RU2497933C2 (en) | 2008-03-13 | 2009-03-13 | Method for conversion of low-grade raw feedstock to high-quality oil fuel |
| KR1020107018801A KR101606496B1 (en) | 2008-03-13 | 2009-03-13 | Method for obtaining light fuel from inferior feedstock |
| PCT/CN2009/000272 WO2009111953A1 (en) | 2008-03-13 | 2009-03-13 | Method for obtaining light fuel from inferior feedstock |
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