CN102373086B - Method for producing light fuel by using gas oil and residual oil - Google Patents
Method for producing light fuel by using gas oil and residual oil Download PDFInfo
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Abstract
The invention discloses a method using gas oil and residual oil to process light fuel. The gas oil, catalytic cracking heavy oil and hydrogen are mixed to enter a first hydrogenation reaction area to react, the produced oil after the reaction and residual oil raw materials are mixed to react in a second hydrogenation reaction area, the obtained product after the reaction is separated to obtain a liquid phase product and a gas phase product, wherein the gas phase product is purified and pressurized to be fed back to the first hydrogenation reaction area for cycle use, the hydrogenation residual oil in the liquid phase product enters a catalytic cracking device to react, and the catalytic cracking heavy oil in a reaction product is circulated to the first hydrogenation reaction area. The method organically combines the heavy oil hydrotreatment and the catalytic cracking device, can translate inferior gas oil and residual oil into light fuel to the maximum extent, so the liquid yield is improved.
Description
Technical field
The invention belongs to a kind of working method of hydrocarbon ils, a kind of in the situation that there is the method for the refining hydrocarbon ils of hydrogen and a kind of in the situation that there is not the combination of the method for hydrogen cracking hydrocarbon ils specifically.
Background technology
In recent years, along with developing rapidly of national economy, oil consumption presents the gesture of sharp increase, disparities between supply and demand are comparatively outstanding, and the heavy oil demand reduces day by day, and the light oil demand constantly increases, therefore in order sufficiently and reasonably to utilize petroleum resources, oil refining industry must be to the deep processing future development.In order to improve the level of crude oil processing, increase yield of light oil, the heavy oil lighting just becomes oil refining industry at present and one of main task in the future.
Catalytic cracking is one of most important crude oil secondary processing processing method, but, along with the construction of more and more hydroeracking units, the contradiction that hydrocracking and catalytic cracking are contended over raw materials mutually occurred, causes the shortage of the main raw material vacuum gas oil of catalytic cracking.Meanwhile, along with the minimizing of oil fuel demand, residual oil is faced with the strong request of further processing.Therefore process a part of residual oil by existing catalytic cracking unit, become one of effective ways that address the above problem.But owing to generally containing heavy metal and the bituminous matters such as nickel, vanadium in residual oil, can produce and to pollute and to generate a large amount of coke cracking catalyst, so need to also carry out pre-treatment to residual oil raw material, to reduce in raw material sulphur, nitrogen, metal impurities content and to reduce carbon residue.
The another one problem that catalytic cracking process faces is, transformation efficiency and the yield of light oil of existing catalytic cracking unit in order to increase catalytic cracking, usually catalytic cracking heavy oil catalytic cracking unit produced self circulates in catalytic cracking unit, because the hydrogen richness of catalytic cracking heavy oil is low, polycyclic aromatic hydrocarbon content is high, its cracking effect is unsatisfactory, a big chunk of catalytic cracking heavy oil is converted into coke, increase the revivifier load, reduced treatment capacity and the petrol and diesel oil product yield of catalytic cracking unit.
For this problem, CN1382776A discloses a kind of method of residual hydrocracking and catalytically cracking heavy oil, the method is carried out hydrogenation reaction by residual oil at hydrotreater, the hydrogenated residue of gained enters catalytic cracking unit and carries out cracking reaction together with optional vacuum gas oil, the heavy cycle oil of catalytic cracking returns to hydrotreater, and the thing that steams that the distillation slurry oil obtains returns to hydrotreater.The method is organically joined together two devices, residual oil, heavy cycle oil and slurry oil can be converted into to light-end products.The method need to be built the residual hydrogenation equipment of high pressure, and facility investment is large.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of and process gas oil inferior and residual oil by hydrotreatment and catalytic cracking combined technique, produce the method for light Fuel.
Method provided by the invention comprises:
(1) gas oil feedstocks and catalytic cracking heavy oil with enter the first hydroconversion reaction zone after hydrogen mixes and contact and reacted with the hydrofining agent with hydrogenation protecting agent, the agent of hydrogenation diasphaltene successively,
(2) reaction of step (1) gained the first hydroconversion reaction zone generates oil and enters the second hydroconversion reaction zone without separating directly with after residual oil raw material mixes, contact and reacted with residual oil hydrocatalyst, the resultant of reaction separation obtains gaseous stream and liquid phase stream, wherein gaseous stream returns to the first hydroconversion reaction zone and recycles after purifying, boosting, and liquid phase stream obtains gas, hydrogenated gasoline, hydrogenated diesel oil and hydrogenated residue through fractionation;
(3) step (2) gained hydrogenated residue enters catalytic cracking unit, under existing, the cracking conversion catalyst reacted, reaction product isolated obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil, and wherein catalytic cracking heavy oil loops back the first hydroconversion reaction zone of step (1).
The described gas oil feedstocks of step (1) is one or more in atmospheric gas oil, vacuum gas oil, coker gas oil and deasphalted oil.In step (1), the processing condition of the first hydroconversion reaction zone are: hydrogen dividing potential drop 4.0MPa～12.0MPa, preferred 6.0MPa～10.0MPa, 330 ℃～420 ℃ of temperature of reaction, preferably 340 ℃～410 ℃, volume space velocity 0.5h
-1～2.5h
-1, preferred 0.7h
-1～2.0h
-1, hydrogen to oil volume ratio 100～1200, preferably 200～1000.
At least comprise a reactor in step (1) in the first hydroconversion reaction zone; hydrogenation protecting agent and hydrogenation deasphalting medium and hydrofining agent can single bed or minute a plurality of beds be packed in a reactor or a plurality of reactor, the reaction effluent between each reactor is not separated.The first reaction zone catalyzer overall volume of take is benchmark, and the admission space percentage ratio of described hydrogenation protecting agent, the agent of hydrogenation diasphaltene and hydrofining agent is respectively 2%～30%, 5%～50% and 5%～93%.
Described hydrogenation protecting agent is the Raschig ring shape, contain a kind of alumina supporter and load on molybdenum and/or the tungsten on this alumina supporter, and nickel and/or cobalt, the gross weight of hydrogenation protecting agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 1～10 % by weight, and the content of nickel and/or cobalt is 0.5～3 % by weight; Described aluminum oxide is gama-alumina; Described hydrogenation protecting agent pore volume is not less than 0.50ml/g, preferably is not less than 0.60ml/g.This hydrogenation protecting agent has low coke content, low pore volume rate of descent, good activity stability and high intensity.Owing to inevitably can carrying the powder of catalytic cracking catalyst in catalytic cracking heavy oil; therefore the present invention is in the larger hydrogenation protecting agent of the top of the first hydroconversion reaction zone filling voidage; can further remove the tiny catalytic cracking catalyst powder of carrying secretly in raw material; the foulant of easy green coke in while energy effective elimination raw material; reach the purpose of protection hydrogenation Primary Catalysts, guarantee the hydrotreater long-time running.
The agent of described hydrogenation diasphaltene is the butterfly type, contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of hydrogenation diasphaltene agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 % by weight, and the content of nickel and/or cobalt is 0.3～10 % by weight, and carrier is aluminum oxide and optional silicon oxide; Described hydrogenation diasphaltene agent pore volume is not less than 0.60ml/g, preferably is not less than 0.70ml/g.The asphalt content of conventional wax oil hydrogenation refining plant design charging generally should be less than 500 μ g/g, and the asphalt content in catalytic cracking heavy oil is in 3000 μ g/g left and right, far above conventional Wax Oil Hydrogenation Unit design charging requirement.Bituminous matter is component the heaviest in catalytic cracking heavy oil, it is green coke precursor main in catalytic cracking heavy oil, molecular dimension often reaches tens more than nanometer, easily causes the catalyzer coking and deactivation, affects the work-ing life of catalyst activity stability and shortening catalyzer.Therefore to load the hydrogenation diasphaltene agent of large pore volume in hydrogenation protecting agent back, make the bituminous matter in raw material can obtain partly removing, to reach the purpose of protection rear portion hydrofining agent.
Described hydrofining agent is the butterfly type, contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of hydrofining agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 10～40 % by weight, and the content of nickel and/or cobalt is 0.3～7 % by weight, and carrier is aluminum oxide and optional silicon oxide; Described hydrofining agent pore volume is not less than 0.25ml/g, preferably is not less than 0.30ml/g.At hydrogenation diasphaltene catalyzer back filling Hydrobon catalyst, this catalyzer has much higher Polycyclic aromatic hydrocarbons saturated activity, has high desulfurization and denitrification activity simultaneously.
Described residual oil raw material is long residuum and/or vacuum residuum, and the second hydroconversion reaction zone liquid phase feeding integral body of take is benchmark, and the weight percent of residual oil raw material is 5%～50%.Liquid stream and the residual oil raw material of described the second hydroconversion reaction zone liquid phase feeding in the first hydroconversion reaction zone resultant forms.
The processing condition of the second hydroconversion reaction zone are: hydrogen dividing potential drop 4.0MPa～12.0MPa, preferred 6.0MPa～11.0MPa, 330 ℃～420 ℃ of temperature of reaction, preferably 340 ℃～410 ℃, volume space velocity 0.2h
-1～1.5h
-1, preferred 0.3h
-1～1.2h
-1, hydrogen to oil volume ratio 100～1200, preferably 200～1000.
The catalyzer loaded in the second hydroconversion reaction zone in step (1) can be various existing residual oil hydrocatalysts, its active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, carrier is aluminum oxide, silicon-dioxide or amorphous aluminum silicide, and wherein aluminum oxide is the most frequently used carrier.Preferably residual oil hydrocatalyst, according to the direction of reactant flow, loads residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst and catalyst for hydrotreatment of residual oil successively.Has a reactor in described the second hydroconversion reaction zone at least; residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst and catalyst for hydrotreatment of residual oil can single bed or minute a plurality of beds be packed in a reactor or a plurality of reactor, the reaction effluent between each reactor is not separated.The second hydroconversion reaction zone catalyzer overall volume of take is benchmark, and wherein the admission space percentage ratio of residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst and catalyst for hydrotreatment of residual oil is respectively 2%～10%, 20%～70%, 20%～78%.
In step (2) catalytic cracking unit: the first reaction zone that the hydrogenated residue of preheating enters catalytic conversion reactor under the castering action of water vapor contacts with hot regeneration catalyzing conversion catalyst, in temperature of reaction, it is 510 ℃～650 ℃, reaction times is 0.05 second～1.0 seconds, the weight ratio of catalyzer and stock oil (hereinafter to be referred as agent-oil ratio) is 3～15: 1, the weight ratio of water vapor and stock oil (hereinafter to be referred as water-oil ratio) is 0.03～0.3: 1, the macromole cracking reaction occurs under the condition that pressure is 130kPa～450kPa, remove metal in inferior feedstock oil, sulphur, at least one impurity in nitrogen, the second reaction zone that the oil gas generated and used catalyst enter catalytic conversion reactor is to carry out cracking reaction, hydrogen transfer reactions and isomerization reaction under 420 ℃～550 ℃, the reaction times condition that is 1.5 seconds～20 seconds in temperature of reaction, reaction product isolated obtains dry gas, propylene, propane, C
4hydrocarbon, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil.
Catalytically cracked gasoline described in step (3) or catalytic cracking diesel oil boiling range are adjusted according to actual needs, are not limited only to full range gasoline or diesel oil.The boiling range of gained catalytic cracking heavy oil is 260 ℃～550 ℃, take the catalytic cracking fresh feed as benchmark, and the shared weight percent of catalytic cracking heavy oil is 12%～60%, preferably 15%～40%.
Described catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0.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 preferably heavy % of 20 heavy %-80, large pore zeolite accounts for the heavy % of 0 heavy %-100 of zeolite gross weight, the preferably heavy % of 20 heavy %-80.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification to the transition metal such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel for above-mentioned mesopore zeolite.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, and the more detailed description of relevant ZSM-5 is referring to US3, and 702,886.The mixture of one or more in this group zeolite that super steady Y, the high silicon Y that large pore zeolite selects free Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods to obtain forms.
Advantage of the present invention is:
1, the present invention organically joins together heavy-oil hydrogenation processing and catalytic cracking unit, gas oil inferior and residual oil can be converted into to light-end products to greatest extent, has improved liquid yield.Can make existing catalytic cracking unit mix the residual oil of refining 5～50 heavy %, widen the catalytically cracked material source, alleviate the contradiction that hydrocracking and catalytic cracking are contended over raw materials, improve the working depth of residual oil simultaneously.
2, in the present invention, gas oil and catalytic cracking heavy oil are first in the independent hydrotreatment of the first reaction zone.Because there is no the interference of residual oil, therefore can obtain sufficient hydrotreatment, sulphur, nitrogen decreasing ratio and aromatic saturation rate are high.The larger residual oil hydrocatalyst of filling pore volume in second reaction zone.In residual oil, the macromole such as colloid, bituminous matter also can enter into the catalyzer duct, makes heavy metal, sulphur, nitrogen and carbon residue in residual oil also can obtain most removing, thereby produces qualified catalytically cracked material.
3, the present invention's the first hydroconversion reaction zone (gas oil hydrotreatment) and the second hydroconversion reaction zone (residual hydrocracking) share a hydrogen gas system and share one after separation system, saved a large amount of investment costs and process cost.In addition, method provided by the invention is compared with conventional residual hydrocracking technology, and pressure is low, volume space velocity is high, and cost of investment is low.
The accompanying drawing explanation
Accompanying drawing is that the present invention produces the method process flow diagram of light Fuel with gas oil and residual oil,
Embodiment
Below by accompanying drawing, method of the present invention is further described, but not thereby limiting the invention.As shown in the figure:
After gas oil feedstocks and the catalytic cracking heavy oil mixing from pipeline 25 from pipeline 1; enter the first hydrogenator 3 (the first hydroconversion reaction zone) with together with hydrogen from pipeline 13 through pipeline 2; contact and reacted with the hydrofining agent with hydrogenation protecting agent, the agent of hydrogenation diasphaltene successively; its reaction product by pipeline 4 with after residual oil raw material from pipeline 5 mixes; enter the second hydrogenator 7 (the second hydroconversion reaction zone) through pipeline 6, further reacted under the effect of residual oil hydrocatalyst.The reaction product of the second hydrogenator 7 enters high-pressure separator 9 through pipeline 8, separate and obtain gaseous stream and liquid phase stream, wherein gaseous stream enters circulating hydrogen compressor 11 through pipeline 10 and is boosted, and after boosting, with new hydrogen from pipeline 12, mixes through pipeline 13 and stock oil and is mixed into the first hydroconversion reaction zone.The liquid phase stream of high-pressure separator 9 gained enters atmospheric fractional tower 15 through pipeline 14, separates and obtains gas, hydrogenated gasoline, hydrogenated diesel oil and hydrogenated residue.Wherein gas, hydrogenated gasoline and hydrogenated diesel oil go out device by pipeline 16,17 and 18 respectively.Hydrogenated residue enters catalytic cracking unit 20 through pipeline 19, under catalytic converting catalyst exists, carries out cracking reaction, obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil.Wherein dry gas, liquefied gas, catalytically cracked gasoline and catalytic cracking diesel oil go out device by pipeline 21,22,23 and 24 respectively.Catalytic cracking heavy oil loops back the first hydroconversion reaction zone through pipeline 25.
The following examples will be further described the present invention, but therefore not limit the present invention.
In embodiment, the essential property of gas oil feedstocks used and residual oil raw material is as shown in table 1.The trade names of the hydrogenation protecting agent of loading in the first hydroconversion reaction zone are respectively RG-10B, by Sinopec catalyzer branch office Chang Ling catalyst plant, are produced, by laboratory, prepared by the agent of hydrogenation diasphaltene and hydrofining agent, and physico-chemical property is in Table 2.The trade names of the residual hydrogenation protective material loaded in the second hydroconversion reaction zone, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer are respectively RG-10A, RDM-2B, RMS-1B, by Sinopec catalyzer branch office Chang Ling catalyst plant, produce.The catalytic converting catalyst that catalytic cracking unit is used is by the Shandong catalyst plant production of catalyzer branch office of China Petrochemical Industry, and trade names are MLC-500.
Embodiment 1
Gas oil, catalytic cracking heavy oil enter the first hydroconversion reaction zone with the mixture of hydrogen and contact and reacted with hydrogenation protecting agent, the agent of hydrogenation diasphaltene, Hydrobon catalyst successively, the first hydroconversion reaction zone catalyst volume of take is benchmark, and the admission space percentage ratio of hydrogenation protecting agent, the agent of hydrogenation diasphaltene and Hydrobon catalyst is respectively 8 volume %, 15 volume % and 77 volume %; Its resultant of reaction enters the second hydroconversion reaction zone without separating directly with after residual oil mixes, and the second hydroconversion reaction zone liquid phase feeding integral body of take is benchmark, and the residual oil weight percent that enters the second hydroconversion reaction zone is 30 heavy %.Mixing raw material contacts and is reacted with catalyst for hydrotreatment of residual oil with residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst successively; the second hydroconversion reaction zone catalyst volume of take is benchmark; the admission space percentage ratio of hydrogenation protecting agent, Hydrodemetalation catalyst and hydrotreating catalyst is respectively 10 volume %; 40 volume %, 50 volume %.
The resultant of reaction of the second hydroconversion reaction zone, after refrigerated separation, obtains hydrogen-rich gas and product liquid.Wherein gas-phase product returns to the first hydroconversion reaction zone and recycles after purifying, boosting.The frequent pressure fractionating of liquid product obtains gas, hydrogenated gasoline, hydrogenated diesel oil and hydrogenated residue.Hydrogenated residue enters catalytic cracking unit, under existing, catalytic converting catalyst reacted, reaction product isolated obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil, wherein the gained catalytic cracking heavy oil accounts for 30 % by weight of catalytic cracking charging, and loops back hydrogenation unit the first hydroconversion reaction zone.
The present embodiment the first hydroconversion reaction zone, the second hydroconversion reaction zone and catalytic cracking unit reaction conditions are as shown in table 3.The total product of combination process distributes (two device product sums) in Table 3.
Embodiment 2
The technical process of the present embodiment is identical with embodiment 1.As different from Example 1, the second hydroconversion reaction zone liquid phase feeding integral body of take is benchmark, and the residual oil weight percent that enters the second hydroconversion reaction zone is 15 heavy %.The first reaction zone catalyst volume of take is benchmark, and the admission space percentage ratio of hydrogenation protecting agent, the agent of hydrogenation diasphaltene and Hydrobon catalyst is respectively 5 volume %, 12 volume % and 83 volume %; Take the second reaction zone catalyst volume as benchmark, and the admission space percentage ratio of residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst and catalyst for hydrotreatment of residual oil is respectively 5 volume %, 35 volume %, 60 volume %.In the present embodiment, the gained catalytic cracking heavy oil accounts for 20 % by weight of catalytic cracking charging,
The present embodiment the first hydroconversion reaction zone, the second hydroconversion reaction zone and catalytic cracking unit reaction conditions are as shown in table 3.The total product of combination process distributes (two device product sums) in Table 3.
From table 3, embodiment 1 and embodiment 2 have all reached higher liquid (liquefied gas+gasoline+diesel oil) yield, are respectively 88.21% and 91.09%.Illustrate that the present invention organically joins together hydrotreatment and catalytic cracking unit, gas oil inferior and residual oil can be converted into to light-end products to greatest extent, improved the liquid yield of catalytic cracking unit.
Table 1
| The stock oil title | Gas oil | Residual oil |
| Density (20 ℃), g/cm 3 | 0.9334 | 1.0108 |
| Viscosity (100 ℃), mm 2/s | 12.30 | 638.0 |
| Carbon residue, heavy % | 0.52 | 19.2 |
| Sulphur, heavy % | 3.1 | 4.3 |
| Nitrogen, heavy % | 0.13 | 0.26 |
| Carbon, heavy % | 85.15 | 84.85 |
| Hydrogen, heavy % | 11.86 | 10.48 |
| Metal content, ppm | ||
| Nickel | 0.1 | 22.9 |
| Vanadium | 0.5 | 75.6 |
| Four components, heavy % | ||
| Stable hydrocarbon | 56.6 | 15.7 |
| Aromatic hydrocarbons | 40.2 | 53.5 |
| Colloid | 3.2 | 24.7 |
| Bituminous matter (C 7Insolubles) | - | 6.1 |
Table 2
| Catalyzer | The agent of hydrogenation diasphaltene | The hydrofining agent |
| Chemical constitution, % by weight | ||
| Nickel oxide | 1.1 | 2.8 |
| Molybdenum oxide | 6.2 | / |
| Tungsten oxide 99.999 | / | 26.2 |
| Physical properties: | ||
| Specific surface area, m 2/g | 120 | 170 |
| Pore volume, ml/g | 0.71 | 0.33 |
| Crushing strength, N/mm | 11 | 18 |
| Shape | The butterfly type | The butterfly type |
Table 3
Claims (11)
1. a method of producing light Fuel with gas oil and residual oil comprises:
(1) gas oil feedstocks and catalytic cracking heavy oil with enter the first hydroconversion reaction zone after hydrogen mixes and contact and reacted with the hydrofining agent with hydrogenation protecting agent, the agent of hydrogenation diasphaltene successively,
(2) reaction of step (1) gained the first hydroconversion reaction zone generates oil and enters the second hydroconversion reaction zone without separating directly with after residual oil raw material mixes, contact and reacted with residual oil hydrocatalyst, the resultant of reaction separation obtains gaseous stream and liquid phase stream, wherein gaseous stream returns to the first hydroconversion reaction zone and recycles after purifying, boosting, and liquid phase stream obtains gas, hydrogenated gasoline, hydrogenated diesel oil and hydrogenated residue through fractionation;
(3) step (2) gained hydrogenated residue enters catalytic cracking unit, under existing, the cracking conversion catalyst reacted, reaction product isolated obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil, and wherein catalytic cracking heavy oil loops back the first hydroconversion reaction zone of step (1);
The boiling range of described step (3) gained catalytic cracking heavy oil is 260 ℃～550 ℃, take the catalytic cracking fresh feed as benchmark, and the shared weight percent of catalytic cracking heavy oil is 12%～60%.
2. in accordance with the method for claim 1, it is characterized in that, described gas oil feedstocks is one or more in atmospheric gas oil, vacuum gas oil, coker gas oil and deasphalted oil.
3. in accordance with the method for claim 1, it is characterized in that, the processing condition of described the first hydroconversion reaction zone are: hydrogen dividing potential drop 4.0MPa～12.0MPa, 330 ℃～420 ℃ of temperature of reaction, volume space velocity 0.5h
-1～2.5h
-1, hydrogen to oil volume ratio 100～1200.
4. in accordance with the method for claim 1; it is characterized in that; described to take the first hydroconversion reaction zone catalyzer overall volume be benchmark, and the admission space percentage ratio of described hydrogenation protecting agent, the agent of hydrogenation diasphaltene and hydrofining agent is respectively 2%～30%, 5%～50% and 5%～93%.
5. in accordance with the method for claim 1, it is characterized in that, described hydrogenation protecting agent is the Raschig ring shape, contain a kind of alumina supporter and load on molybdenum and/or the tungsten on this alumina supporter, and nickel and/or cobalt, the gross weight of hydrogenation protecting agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 1～10 % by weight, and the content of nickel and/or cobalt is 0.5～3 % by weight; Described aluminum oxide is gama-alumina; Described hydrogenation protecting agent pore volume is not less than 0.50ml/g.
6. in accordance with the method for claim 1, it is characterized in that, the agent of described hydrogenation diasphaltene is the butterfly type, contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of hydrogenation diasphaltene agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 % by weight, and the content of nickel and/or cobalt is 0.3～10 % by weight, and carrier is aluminum oxide and optional silicon oxide; Described hydrogenation diasphaltene agent pore volume is not less than 0.60ml/g.
7. in accordance with the method for claim 1, it is characterized in that, described hydrofining agent is the butterfly type, contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of hydrofining agent of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 10～40 % by weight, and the content of nickel and/or cobalt is 0.3～7 % by weight, and carrier is aluminum oxide and optional silicon oxide; Described hydrofining agent pore volume is not less than 0.25ml/g.
8. in accordance with the method for claim 1, it is characterized in that, described residual oil raw material is long residuum and/or vacuum residuum, and the second hydroconversion reaction zone liquid phase feeding integral body of take is benchmark, and the weight percent of residual oil raw material is 5%～50%.
9. in accordance with the method for claim 1, it is characterized in that, the processing condition of described the second hydroconversion reaction zone are: hydrogen dividing potential drop 4.0MPa～12.0MPa, 330 ℃～420 ℃ of temperature of reaction, volume space velocity 0.2h
-1～1.5h
-1, hydrogen to oil volume ratio 100～1200.
10. in accordance with the method for claim 1, it is characterized in that, in described step (3) catalytic cracking unit: the first reaction zone that the hydrogenated residue of preheating enters catalytic conversion reactor under the castering action of water vapor contacts with hot regeneration catalyzing conversion catalyst, and in temperature of reaction, be that the weight ratio that 510 ℃～650 ℃, reaction times are 0.05 second～1.0 seconds, catalyzer and stock oil is 3～15: 1, the weight ratio of water vapor and stock oil is 0.03～0.3: the macromole cracking reaction occurs under the condition that 1, pressure is 130kPa～450kPa; The oil gas generated and the first reaction zone enter the second reaction zone of catalytic conversion reactor with the catalytic converting catalyst of mistake, in temperature of reaction, be to carry out cracking reaction, hydrogen transfer reactions and isomerization reaction under 420 ℃～550 ℃, the reaction times condition that is 1.5 seconds～20 seconds.
11. in accordance with the method for claim 1, it is characterized in that, in described step (3), catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % in the heavy % of zeolite 1～50 heavy %, the heavy % of inorganic oxide 5～99 heavy %, the heavy % of clay 0～70.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382776A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
| CN100577773C (en) * | 2006-02-14 | 2010-01-06 | 中国石油化工股份有限公司 | Gas oil and residual oil hydrotreating process for producing catalytically cracked material |
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