CN104560166B - A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline - Google Patents
A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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Abstract
A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline, catalytic cracking light cycle oil obtains light fraction and heavy distillat through cutting, wherein heavy distillat obtains hydrogenation heavy distillat through hydrotreatment, light fraction, hydrogenation heavy distillat separately enter the secondary riser reactor of catalytic cracking unit, heavy petroleum hydrocarbon enters the main riser reactor of catalytic cracking unit, under catalytic cracking catalyst exists, carry out cracking reaction, reaction product isolated obtains comprising the product of gasoline, light cycle oil. The method enters the layering in secondary riser reactor of the heavy distillat after the light fraction of light cycle oil and hydrogenation, can optimize to greatest extent and meet the required harsh conditions of light cycle oil different fractions catalytic cracking reaction, thereby farthest produce high-octane catalytic gasoline.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon in the situation that not there is not hydrogen, more specificallySaying, is a kind of catalysis conversion method of being produced high-knock rating gasoline by heavy petroleum hydrocarbon.
Background technology
Along with the development of crude oil heaviness and the rapid growth of market to light-end products demand, in China, doFor the catalytic cracking technology of heavy oil lighting is rapidly developed. But, a fact must facingThe quality that is catalytic cracking diesel oil (or title " light cycle oil ") is but always relatively poor, and density is large, virtueHydrocarbon content is high, and Cetane number is low, even be also difficult to reach increasingly stringent by diesel oil hydrogenation modification technologyDiesel oil regulation. How solving catalytic cracking light cycle oil is an increasingly serious problem. Deposit simultaneouslyAnother one problem be domestic gasoline product chronic shortage, and catalytically cracked gasoline accounts for gasoline product80%. Therefore, how to realize heavy charge by catalytic cracking process and maximize production higher octaneValue gasoline and not produce light cycle oil may be the new way addressing the above problem.
US4585545 has disclosed one full catalytic cracking light cycle oil cut has first been carried out to hydrotreatment,The hydrogenated diesel oil obtaining goes catalytic cracking to produce the catalysis conversion method that is rich in mononuclear aromatics gasoline again.
CN1422327A discloses a kind of method of catalytic cracking light cycle oil upgrading, is by with heavyThe light cycle oil that the first catalytic cracking unit that oil is raw material is produced carries out deep hydrogenation, the hydrogenation obtainingRecycle oil enters the second catalytic cracking unit again. On the basis of the method, CN1423689A emphasizesCatalyst in two catalytic cracking units requires the aperture of selecting shape zeolite and about 5-50% containing 50-95%Be more than or equal to the large pore zeolite of about 0.7nm, optionally to improve light olefin productive rate.
CN1466619A discloses a kind of method for transformation of catalytic cracking light cycle oil, is that catalysis is splitChange riser reactor and be divided into two of upstream and downstream reaction zone, wherein mink cell focus injects catchment, itsThe hydrogenation recycle oil that catalytic cracking production light cycle oil obtains after hydrotreatment injects upstream. At thisOn the basis of method, the charging in CN1425054A method middle and lower reaches district is except hydrogenation recycle oil, alsoIncrease naphtha. In the method, not only hydrogen consumption is high, and hydrogenation recycle oil can be tight in upstream reactionGhost image rings the conversion of the mink cell focus in downstream.
Can find from disclosed document above, that processes for catalytic cracking light cycle oil is importantOne of approach is that it is first carried out to hydrotreatment, and then catalytic cracking. It must be noted that, gently followTherefore how no matter whether hydrogenation of ring oil, compares with the large molecule of mink cell focus, and its molecule is little, bond energy is large,The operating parameter of controlling catalytic cracking is one of key of light cycle oil processing. If light cycle oil simultaneouslyCarry out hydrogenation, the operation control of hydrogenation process is also one of key of light cycle oil processing. In addition, heavyIn matter petroleum hydrocarbon catalytic cracking process, maximize production high-knock rating gasoline and do not produce light cycle oil,Must take into account the selective catalysis cracking how consideration realizes heavy petroleum hydrocarbon and light cycle oil.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of is maximized by heavy petroleum hydrocarbonProduce the catalysis conversion method of high-knock rating gasoline.
Catalysis conversion method provided by the invention comprises:
(1) catalytic cracking light cycle oil obtains light fraction and heavy distillat through cutting;
(2) the described heavy distillat of step (1) is carried out hydrogenation under hydrogen and hydrotreating catalyst existenceProcessing reaction, reaction product isolated obtains hydrogenation heavy distillat;
(3) the described light fraction of step (1), the described hydrogenation heavy distillat of step (2) divide from bottom to upLayer enters the secondary riser reactor of catalytic cracking unit, under catalytic cracking catalyst exists, carries out catalysisCracking reaction, separate catalytic cracking catalyst to be generated and reaction oil gas, and wherein reaction oil gas is through separatingTo the product that comprises gasoline, light cycle oil;
(4) heavy crude hydrocarbon feed enters the main riser reactor of catalytic cracking unit, splits in catalysisChange under catalyst existence and carry out catalytic cracking reaction, separate catalytic cracking catalyst to be generated and reaction oil gas,Wherein reaction oil gas is isolated to the product that comprises gasoline, light cycle oil;
(5) step (3), (4) described catalytic cracking catalyst to be generated gained after stripping, regenerationRegeneration catalyzing Cracking catalyst is returned to riser reactor and is recycled.
The described catalytic cracking light cycle oil of step (1) is selected from allocatalysis cracking unit and produces light circulationOil is or/and this method catalytic cracking unit step (3) light cycle oil that produces, preferably allocatalysis crackingDevice the light cycle oil that produces and this method catalytic cracking unit step (3) light cycle oil that produces. Above-mentionedIn method, step (3) is called light cycle oil recycle ratio with the mass ratio of heavy crude hydrocarbon feed.
Method provided by the invention is specific as follows:
Catalytic cracking light cycle oil enters independent fractionating column and cuts, and cutting temperature is controlled at250～260 DEG C, preferably cutting temperature is 260 DEG C, obtains respectively not high from top and the bottom of fractionating columnIn the light fraction of this cutting temperature with higher than the heavy distillat of this cutting temperature.
Hydrotreater is removed in described heavy distillat, under hydrogen and hydrogenation catalyst existence, carries out hydrogenation placeReason reaction, hydroprocessing condition is: hydrogen dividing potential drop 5.0～22.0MPa, preferably 8.0～15.0MPa; InsteadAnswer 330～450 DEG C of temperature, preferably 340～380 DEG C; Volume space velocity 0.1～10.0 hour-1, hydrogen oil volumeThan 100～2000Nm3/m3. Reaction product isolated obtains heating up in a steamer of 260 DEG C of 250 DEG C of preferred > of initial boiling point >Point, or claim hydrogenated diesel oil, hydrogenation heavy distillat. In described hydrogenation heavy distillat, double ring arene content wants≤20Heavy %, the heavy % in preferably≤10.
Described activity of hydrocatalyst metal component be selected from group vib metal and/or group VIII non-Noble metal, carrier is selected from aluminium oxide, silica, amorphous aluminum silicide any one or several. DescribedGroup vib metal is molybdenum or/and tungsten, and group VIII base metal is that nickel is or/and cobalt. Active metal groupDivide the combination of preferred nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
Enter carrying in advance of riser reactor bottom from a part of high-temperature regenerated catalyst of regeneratorRise section, through pre-lift medium lifting, up, with light fraction haptoreaction, up; Subsequently with hydrogenationHeavy distillat haptoreaction, oil gas, catalyst mixture are up, then with heavy crude hydrocarbon feed, comeFrom another part high-temperature regenerated catalyst haptoreaction of regenerator; Reaction oil gas from riser outFinally enter main fractionating tower and absorbing-stabilizing system subsequently and then separation. Wherein main fractionating tower outLight cycle oil can enter newly-increased light cycle oil fractionating column and cut, the light cycle oil that cutting obtainsLight fraction direct circulation returns secondary riser, and hydrotreatment dress is removed in the light cycle oil heavy distillat that cutting obtainsPut that to carry out hydrogenation saturated, and light cycle oil heavy distillat after hydrogenation loops back secondary riser.
The light fraction of light cycle oil and hydrogenation heavy distillat preferably separately enter separately catalytic cracking unitSecondary riser reactor, wherein light fraction enters from lower floor's nozzle (upstream) of riser, and hydrogenationHeavy distillat enters from the upper strata nozzle (downstream) of riser. The distance of upper and lower layer nozzle is anti-to controlAnswering the time of staying of oil gas in two-layer nozzle distance is to be advisable for 0.01～3 second, preferably 0.05～1 second.The advantage that light fraction and hydrogenation heavy distillat layering enter is can optimize to meet different fractions catalytic crackingReaction condition, thereby realize farthest transform.
The reaction condition of the main riser reactor of catalytic cracking unit is not particularly limited, as conventional heavy oilCatalytic cracking condition, reaction temperature is 450-550 DEG C, agent oil quality is than 4～8, the oil gas time of staying2～4 seconds, pressure (absolute pressure) 0.15～0.4MPa, the weight ratio of water vapour and raw material is 0.02～0.08;Be that heavy petroleum hydrocarbon is also not particularly limited to the raw material of main riser reactor, conventional heavy charge is equalCan. The described heavy crude hydrocarbon feed of step (3) be selected from straight-run gas oil, wax tailings, deasphalted oil,One or more in hydrofined oil, hydrocracking tail oil, decompression residuum, reduced crude.
The reaction condition of secondary riser reactor is: reaction temperature is 520～650 DEG C, preferably550～590 DEG C; Agent oil quality is than 5～100, and preferably 8～50; 1～10 second oil gas time of staying, preferably2～8 seconds; Pressure (absolute pressure) 0.15～0.4MPa; The weight ratio of water vapour and raw material is 0.01～0.5Preferably 0.02～0.2.
The equilibrium catalyst agent activity (MAT) >=60 of catalytic cracking unit, preferably >=62.
The described secondary riser reactor of step (3), the described main riser reactor of step (4), beIsometrical riser reactor or reducing riser reactor. Secondary riser reactor reacts with main riserDevice can share a set of settler, main fractionating tower, absorbing-stabilizing system, stripper, regenerator, alsoCan use settler, main fractionating tower, absorbing-stabilizing system, stripper, regenerator separately.
Catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay. The content of each componentBe respectively: the heavy % of zeolite 10～50, the heavy % of inorganic oxide 5～90, the heavy % of clay 0～70. WhereinActive component is to be selected to contain or do not contain the one, two in Y, HY, USY or the Beta zeolite of rare earthKind or multiple.
The invention has the advantages that:
1, can thoroughly realize heavy crude hydrocarbon catalytic cracking and not produce light cycle oil.
2, catalytic cracking unit light cycle oil is first cut, and wherein hydrogenation is removed in heavy distillat, canReduce to greatest extent hydrogen consumption;
3, adopt the major and minor riser of catalytic cracking unit to process respectively heavy petroleum hydrocarbon and light cycle oil,Contribute to optimize respectively the operating condition of the two, the maximization that realizes the two transforms.
4, the heavy distillat layering in secondary riser reactor after light fraction and the hydrogenation of light cycle oil is enteredEnter, can optimize to greatest extent and meet the required harshness of light cycle oil different fractions catalytic cracking reactionCondition, thus high-octane catalytic gasoline farthest produced.
Brief description of the drawings
Fig. 1 is the catalysis conversion method flow process signal of production high-octane rating catalytic gasoline provided by the inventionFigure.
Detailed description of the invention
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention not therefore andBe subject to any restriction.
Accompanying drawing is catalysis conversion method schematic flow sheet provided by the invention.
Fig. 1 is the schematic flow sheet of preferred forms of the present invention, but does not limit the present invention. EquipmentWith the shape of pipeline, the restriction that size is not subject to accompanying drawing, but determine as the case may be. Each in accompanying drawingNumbering is described as follows:
1,3-5,7,13,15-16,18-20,22 all represent pipeline; 2 is light cycle oil fractionating column;6 is hydrotreater; 10 is catalytic cracking unit; 8,9,21 is feed nozzle; 11 is secondaryRiser reactor; 12 is main riser reactor; 14 is main fractionating tower; 17 for absorbing stability seriesSystem.
Below in conjunction with accompanying drawing, preferred forms provided by the present invention is further described.
Heavy crude hydrocarbon feed enters the main riser reactor 12 of catalytic cracking unit 10 through nozzle 21Carry out catalytic cracking reaction, reaction oil gas enters main fractionating tower 14 through pipeline 13, from main fractionating tower 14Slurry oil out through pipeline 15 as product discharger; From main fractionating tower 14 oil gas out through pipeLine 16 enters follow-up absorbing-stabilizing system 17 and further separates and obtain product dry gas, liquefied gas and heightOctane number gasoline, respectively from pipeline 18,19,20 ejectors; And out light of main fractionating tower 14Recycle oil enters light cycle oil fractionating column 2 through pipeline 22,1 and cuts, and obtains≤260 DEG C lightThe heavy distillat that cut and > are 260 DEG C. The light fraction of wherein≤260 DEG C enters Catalytic Cracking Unit of Measure through pipeline 3Should install lower floor's nozzle 9 of 10 secondary riser reactor 11; And the heavy distillat of 260 DEG C of > is through pipeline4 enter hydrotreater 6, and hydrogen is introduced hydrotreater 6 through pipeline 5 simultaneously. After hydrogenationThe heavy distillat of product hydrogenation also enters the secondary riser reactor of catalytic cracking reaction device 10 through pipeline 711 upper strata nozzle 8. Light fraction and hydrogenation heavy distillat in secondary riser reactor in Cracking catalystHave lower generation catalytic cracking reaction, reaction oil gas also enters main fractionating tower 14 through pipeline 13 and goes to carry outLater separation.
The following examples will be further described the present invention, but not thereby limiting the invention.In embodiment, in hydrotreatment fixed bed reactors, the hydrotreating catalyst business trade mark of filling isRN-32V, the protective agent business trade mark is RG-1, hydrotreating catalyst and protectant admission spaceRatio is 95:5, produces by Sinopec catalyst branch company.
The physico-chemical property of catalyst that in embodiment, comparative example, catalytic cracking unit uses is in table 1, itsThe business trade mark is HAC, and by Sinopec catalyst, branch company produces.
The heavy crude hydrocarbon feed using in embodiment, comparative example is 90 heavy % straight-run gas oils and 10The mixed material of heavy % decompression residuum, its character is listed in table 2.
Embodiment
The method providing in Fig. 1 of the present invention is provided in the present embodiment explanation. Wherein light cycle oil fractionating columnBoiling range cutting temperature is 250 DEG C.
Light cycle oil heavy distillat enters medium-sized hydrotreater, and the experimental condition of hydrotreatment is: hydrogenDividing potential drop 8.0MPa; 360 DEG C of average bed reaction temperatures, volume space velocity 0.5 hour-1, hydrogen oil volumeCompare 1100Nm3/m3. In hydrogenation heavy distillat, double ring arene content is 8.0 heavy %.
The main operating parameters of catalytic cracking unit is in table 3. Light fraction is from lower floor's nozzle of secondary riserEnter, and hydrogenation heavy distillat enters the distance control of upper and lower layer nozzle from the upper strata nozzle of secondary riserThe time of staying of reaction oil gas processed in two-layer nozzle distance is 0.2 second.
Comparative example
In comparative example, catalytic cracking test device only has main riser, there is no secondary riser. In comparative exampleThere is no light cycle oil fractionating column yet. The light cycle oil that in comparative example, main fractionating tower obtains without cutting directlyGo hydrogenation plant to carry out hydrogenation of total effluent, the light cycle oil after hydrogenation is mixed together with heavy crude hydrocarbon feedAfter closing, enter the main riser reactor reaction of catalytic cracking unit. Catalyst and embodiment in comparative exampleIdentical. The operating condition of the catalytic cracking unit of comparative example is in table 3.
The distribution of catalytic cracking product, hydrogen consumption and octane number are in table 4.
Comparative example and comparative example can find, embodiment can obviously reduce hydrogen in hydrogenation processConsumption, hydrogen consumption is reduced to 1.43% from 2.6%; In addition, in comparative example due to the recycle ratio of light cycle oilBe 0.29, far above 0.07 in embodiment, finally cause its energy consumption higher. Can also find simultaneously,Compare ratio, in embodiment, gasoline yield increases percentage point more than 9, simultaneously dry gas and coke yieldObviously reduce. In addition, as can be found from Table 4, compare ratio, the product gasoline in embodiment is pungentAlkane value RON is increased to 95.8 by 92.1.
Table 1HAC catalyst property
Table 2 feedstock oil character
| Feedstock oil title | Mixed material |
| Density (20 DEG C), kg/m3 | 916.8 |
| Freezing point, DEG C | 32 |
| Refractive index (70 DEG C) | 1.4968 |
| Carbon residue, heavy % | 2.67 |
| Mean molecule quantity | 404 |
| Boiling range, DEG C | |
| Initial boiling point | 294 |
| 5% | 361 |
| 10% | 381 |
| 30% | 422 |
| 50% | 451 |
| 70% | 497 |
| Sulfur content, % | 1.1 |
| Nitrogen content, % | 0.24 |
| Hydrogen content, % | 12.6 |
| Tenor, mg/kg | |
| Ni | 6.6 |
| V | 1.2 |
Table 3 operating parameter
Table 4
| Embodiment | Comparative example | |
| Hydrogen consumption, % | 1.43 | 2.6 |
| Energy consumption, kg mark oil/ton raw material | 69 | 76 |
| Product distributes, heavy % | ||
| Dry gas | 3.21 | 5.57 |
| Liquefied gas | 17.61 | 22.58 |
| Gasoline | 65.63 | 56.47 |
| Light diesel fuel | 0.00 | 0.00 |
| Heavy oil | 4.51 | 3.11 |
| Coke | 9.04 | 12.27 |
| Add up to | 100.00 | 100.00 |
| Octane number | ||
| RON | 95.8 | 92.1 |
| MON | 85.2 | 81.6 |
Claims (15)
1. petroleum hydrocarbon is produced a catalysis conversion method for high-knock rating gasoline, it is characterized in that the partyMethod comprises:
(1) catalytic cracking light cycle oil obtains light fraction and heavy distillat through cutting;
(2) the described heavy distillat of step (1) is carried out hydrogenation under hydrogen and hydrotreating catalyst existenceProcessing reaction, reaction product isolated obtains hydrogenation heavy distillat;
(3) the described light fraction of step (1), the described hydrogenation heavy distillat of step (2) divide from bottom to upLayer enters the secondary riser reactor of catalytic cracking unit, under catalytic cracking catalyst exists, carries out catalysisCracking reaction, separate catalytic cracking catalyst to be generated and reaction oil gas, and wherein reaction oil gas is through separatingTo the product that comprises gasoline, light cycle oil;
(4) heavy crude hydrocarbon feed enters the main riser reactor of catalytic cracking unit, splits in catalysisChange under catalyst existence and carry out catalytic cracking reaction, separate catalytic cracking catalyst to be generated and reaction oil gas,Wherein reaction oil gas is isolated to the product that comprises gasoline, light cycle oil;
(5) step (3), (4) described catalytic cracking catalyst to be generated gained after stripping, regenerationRegeneration catalyzing Cracking catalyst is returned to riser reactor and is recycled.
2. according to the method for claim 1, it is characterized in that the described light cycle oil of step (3) returnsStep (1).
3. according to the method for claim 1, it is characterized in that the cutting temperature of described light cycle oil is250～260℃。
4. according to the method for claim 1, it is characterized in that the described hydrotreatment of described step (2)Condition be hydrogen dividing potential drop 5.0～22.0MPa, 330～450 DEG C of reaction temperatures, volume space velocity 0.1～10.0Hour-1, hydrogen to oil volume ratio 100～2000Nm3/m3。
5. according to the method for claim 1, it is characterized in that the described hydrotreatment of described step (2)The active metal component of catalyst is selected from group vib metal and/or group VIII base metal, carrierBe selected from aluminium oxide, silica, amorphous aluminum silicide any one or several.
6. according to the method for claim 5, it is characterized in that described group vib metal be molybdenum or/And tungsten, group VIII base metal is that nickel is or/and cobalt.
7. according to the method for claim 5, it is characterized in that described active metal component be selected from nickel-tungsten,The combination of nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
8. according to the method for claim 1, it is characterized in that double ring arene content in hydrogenation heavy distillatBe not more than 20 heavy %.
9. according to the method for claim 1, it is characterized in that the described secondary riser reaction of step (3)Device, the described main riser reactor of step (4) are that isometrical riser reactor or reducing riser are anti-Answer device.
10. according to the method in claim 1, it is characterized in that light fraction and hydrogenation heavy distillat are independentThe secondary riser reactor that separately enters catalytic cracking unit, wherein light fraction is from the lower floor of secondary riserNozzle enters, and hydrogenation heavy distillat enters from the upper strata nozzle of secondary riser.
11. according to the method in claim 10, the distance that it is characterized in that upper and lower layer nozzle withControlling the time of staying of reaction oil gas in two-layer nozzle distance is 0.01～3 second.
12. according to the method in claim 1, it is characterized in that the reaction bar of secondary riser reactorPart is: reaction temperature is 520～650 DEG C, and agent oil quality is than 5～100,1～10 second oil gas time of staying,Pressure 0.15～0.4MPa, the weight ratio of water vapour and raw material is 0.01～0.5, device equilibrium catalystActivity be not less than 60.
13. according to the method in claim 12, it is characterized in that the reaction of secondary riser reactorCondition is: reaction temperature is 550～590 DEG C, and agent oil quality is than 8～50,2～8 seconds oil gas time of staying,The weight ratio of water vapour and raw material is 0.02～0.2, and the activity of device equilibrium catalyst is not less than 62.
14. according to the method for claim 1, it is characterized in that the described catalytic cracking of step (3) urgesAgent comprises zeolite, inorganic oxide and optional clay, and the content of each component is respectively: zeolite10～50 heavy %, the heavy % of inorganic oxide 5～90, the heavy % of clay 0～70, wherein active component is choosingSelf-contained or not containing the one of Y, HY, USY or the Beta zeolite of rare earth, two or more.
15. according to the method for claim 1, it is characterized in that the described heavy petroleum hydrocarbon of step (3)Raw material be selected from straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil,One or more in decompression residuum, reduced crude.
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Cited By (2)
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| CN109705915B (en) | 2017-10-26 | 2020-05-19 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of isobutane and light aromatic hydrocarbons |
| CN110551527B (en) * | 2018-05-30 | 2021-08-06 | 中国石油化工股份有限公司 | Method for producing gasoline rich in aromatic hydrocarbon |
| CN110551526B (en) * | 2018-05-30 | 2021-08-06 | 中国石油化工股份有限公司 | Processing method of catalytic cracking light cycle oil |
| CN111100710B (en) * | 2018-10-25 | 2022-03-11 | 中国石油化工股份有限公司 | Catalytic cracking method and system |
| CN115895722A (en) * | 2022-09-27 | 2023-04-04 | 中国石油化工股份有限公司 | System for preparing light aromatic hydrocarbon from heavy oil raw material |
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