A kind of catalysis conversion method of producing stop bracket gasoline
Technical field
The present invention is the catalysis conversion method that belongs to hydrocarbon ils under the situation that does not have hydrogen, more particularly, is a kind of catalysis conversion method that increases production stop bracket gasoline.
Background technology
Chinese commodity gasoline more than 80% from FCC (FCC) gasoline.The gasoline that China uses at present is main with No. 93, but the catalytically cracked gasoline octane value is on the low side relatively, does not do mediation and generally is usually less than No. 93.At present the whole world increases the demand of gasoline year by year, U.S. 2007 second and third gasoline consumption peak period in season than the same period in 2006 amplification near 1%, reach 947.5 ten thousand BDs.Along with development of Chinese economy, Chinese gasoline car recoverable amount also increases year by year, and therefore the increasing demand to premium-type gasoline improves.Price at No. 93 gasoline of first week Chinese commodity of in November, 2006 surpasses the U.S. gasoline price same period, explains that the imbalance between supply and demand of Chinese gasoline increases day by day.The alkene and the alkane content of China FCC gasoline are higher, and aromaticity content is lower, and FCC gasoline aromatic hydrocarbons volume content is at 10-25%, and what the existing gasoline standard of distance (GB17930-2006) was limited 40% also has very large space.The inferior quality of most of FCC diesel oil, therefore the use serious environment pollution that directly acts as a fuel need carry out upgrading through means such as unifining, hydrogen cracking, has so just increased the secondary processing expense.Because FCC diesel oil contains more mononuclear aromatics,, not only can meet the need of market and have favorable economic benefit if can be part poor-quality diesel-oil by cut fraction catalyzed conversion stop bracket gasoline.
At present the main means of raising the output gasoline are that its amplification is less to the finely tuning of the cut point of gasoline.Perhaps adopt hydrogenation means fecund gasoline, but the hydrogenation technique cost is higher.
US4; 943; 366 disclose the method that stop bracket gasoline is produced in hydrogen cracking under the MP condition of a kind of 600-1000psig (being roughly equal to 4.1-6.9MPa); This method mainly is to use and comprises macropore crystal aluminium si molecular sieves (like Y zeolite) boiling range 300-650 ℉ (being roughly equal to 149-343 ℃), aromatic hydrocarbon content are not less than 50%, and the api gravity index is not more than 25 light cycle oil hydrogenation and takes off alkyl and produce stop bracket gasoline.
CN1160746A discloses a kind of catalysis conversion method that improves gasoline octane number.This method is with in the upper reaches injecting lift pipe reactor of low octane value gasoline by conventional catalytically cracked material inlet, contacts with high temperature catalyst from revivifier, and be that 600-730 ℃, agent-oil ratio are 6-180 in temperature of reaction, weight hourly space velocity is 1-180h
-1Condition under react.This method can make the octane value of gasoline obviously improve, but the waste of gasoline is bigger.
USP5; 409; 596 disclose a kind of catalysis conversion method that improves the hydrogenated gasoline octane value, and this method is that the gasoline fraction after the unifining is contacted with the catalyzer that contains mesopore zeolite, is that 300-900 ℉ (being roughly equal to 149-482 ℃), weight hourly space velocity are 0.5-10h in temperature of reaction
-1, reaction pressure is that the volume ratio of 50-1500psig (being roughly equal to 0.34-10.3MPa), hydrogen and hydro carbons is that the 0-5000 standard cubic feet per barrel (is roughly equal to 0-890Nm
3/ m
3) condition under, carry out the cracking reaction of normal paraffin, thereby the octane value of gasoline fraction be improved.
The contriver is surprised to find that the mononuclear aromatics content of different boiling range diesel oil is different, and mononuclear aromatics content is along with the increase of boiling range reduces gradually substantially.For example greater than 55 heavy %, boiling range weighs % at 195 ℃ of-215 ℃ of distillate mononuclear aromatics content greater than 45 to boiling range at 175 ℃ of-195 ℃ of distillate mononuclear aromatics content.Its transformation efficiency is higher during the distillate catalysis of being rich in mononuclear aromatics, and gasoline yield is higher, and coke yield is lower.Aromatic hydrocarbons in the gasoline has higher mediation motor-method octane number in harmonic process.Therefore be necessary to develop a kind of method that the poor-quality diesel-oil by cut fraction catalyzed conversion can be produced stop bracket gasoline.
Summary of the invention
The objective of the invention is provides a kind of catalysis conversion method of producing stop bracket gasoline on the basis that the contriver finds.
Method of the present invention is such practical implementation: boiling range is that 160 ℃-260 ℃ feedstock contacts with conventional catalytic cracking catalyst, at 400 ℃-750 ℃ of temperature, weight hourly space velocity 0.1h
-1-600h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalyzer and raw material weight ratio (abbreviation agent-oil ratio) 1-120; The weight ratio of water vapor and raw material is under the 0.05-1.0 condition; In fluidized-bed reactor, carry out cracking reaction; Separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regenerating, and separating reaction oil gas obtains purpose product stop bracket gasoline through separation.
Method of the present invention is except separation obtains purpose product stop bracket gasoline; Also can obtain dry gas, liquefied gas, boiling range and be 160 ℃-260 ℃ cut, heavy gas oil cut (boiling range is 260 ℃-350 ℃) and slurry oil, wherein boiling range is that 160 ℃-260 ℃ cut further reacts as recycle stock.
Described raw material is that boiling range is 160 ℃-260 ℃ a cut; Preferred 180 ℃-240 ℃ cut; Being selected from straight run petrol and diesel oil, catalysis petrol and diesel oil, coking gasoline and diesel, thermally splitting petrol and diesel oil, hydrogenation petrol and diesel oil, the gelatin liquefaction petrol and diesel oil one or more, also can be that boiling range that this device produces is 160 ℃-260 ℃ a cut." petrol and diesel oil " of the present invention refers to meet the mixed fraction of the heavy petrol and the solar oil of above-mentioned boiling range.
Present method is suitable for all types of conventional catalytic cracking catalysts, one or more in the ultrastable Y that its active ingredient is selected from the Y or the HY type zeolite that contain or do not contain rare earth, contain or do not contain rare earth and optional ZSM-5 series zeolite or the optional supersiliceous zeolite with five-membered ring structure that makes with additive method; Conventional catalytic cracking catalyst also can be the amorphous silicon aluminium catalyzer.
The compound reactor that fluidizing reactor according to the invention is selected from fluidized-bed, riser tube, downstriker transfer limes reactor drum, be made up of riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, by the compound reactor that two or more downstriker transfer limess constitute, above-mentioned every kind of reactor drum can be divided into two or more reaction zones.That said fluidized-bed is selected from is fixed fluidized bed, in the dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, Transport Bed, dense phase fluidized bed one or more, and preferred fluidized-bed is dense phase fluidized bed more preferably.Said riser tube be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more, preferred equal diameter riser tube.
The present invention can be on CCU implements separately, also can with the CCU Joint Implementation of the conventional catalytically cracked material of processing.When the present invention implemented separately, basic identical with conventional catalytic cracking process, only needing boiling range was after 160 ℃-260 ℃ the feedstock preheating in the injecting reactor, contacted with catalyzer and reacted.When the present invention implements on conventional CCU; Only need the CCU of routine is slightly done transformation; Making said boiling range is the bottom that 160 ℃-260 ℃ feedstock gets into conventional catalyst cracker, and perhaps conventional catalytically cracked material together gets into reactor drum and reacts.When the present invention with processing conventional catalytically cracked material the CCU Joint Implementation time; Said boiling range is that 160 ℃-260 ℃ feedstock and conventional catalytically cracked material carries out in reactor drum separately respectively; And the stripping process of the separation of the separating of reaction oil gas and catalyzer, reaction product and reaction back carbon-bearing catalyzer can be that above-mentioned two bursts of reactant flow are carried out separately separately, also can two bursts of reactant flow combines to carry out.The regenerative process of reclaimable catalyst is to carry out jointly, uses a cover regeneration system rapidly to get final product.
The present invention compared with prior art has following unforeseeable technique effect:
1, the cut that can be produced from hydrocarbon production processes such as air distillation, coking, catalytic cracking, viscosity breaking, gelatin liquefactions of inferior raw material provided by the invention;
When the cut freshening that 2, adopts method provided by the present invention to be generated with CCU itself was produced gasoline, gasoline yield increased 2-8 percentage point, and gasoline octane rating also increases significantly.
When 3, adopting method provided by the present invention to produce gasoline, gasoline yield is up to 55 heavy %, and gasoline octane rating is up to 94;
4, the present invention promptly can implement separately, also can with the CCU Joint Implementation;
When 5, adopting method catalyzed conversion heavy feed stock provided by the present invention, can production part small-numerator olefin, like ethene, propylene etc.
Description of drawings
Accompanying drawing is the schematic flow sheet of the catalysis conversion method of production stop bracket gasoline provided by the invention.
Embodiment
The preferred embodiment of the present invention is and the CCU Joint Implementation of processing conventional catalytically cracked material.
Heavy feed stock contacts with conventional catalytic cracking catalyst, at 400 ℃-750 ℃ of temperature, weight hourly space velocity 0.1h
-1-600h
-1, reaction pressure 0.10MPa-1.0MPa, catalyzer and raw material weight ratio 1-120; The weight ratio of water vapor and raw material is under the 0.05-1.0 condition; In fluidized-bed reactor, carry out cracking reaction, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regenerating; Separating reaction oil gas obtains purpose product stop bracket gasoline and cracking material again through separation, wherein again the cracking material to comprise boiling range be 160 ℃-260 ℃ cut.
Described heavy feed stock is conventional catalytically cracked material; Be petroleum hydrocarbon and/or other MO, wherein petroleum hydrocarbon is selected from a kind of in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum or more than one mixture wherein.
Described heavy feed stock and boiling range are 160 ℃-260 ℃ cut charging or charging respectively together; Described heavy feed stock and boiling range are that 160 ℃-260 ℃ cut advances same reactor drum or advances different reactor drums respectively.
Below in conjunction with accompanying drawing method provided by the present invention is further explained, but therefore do not limited the present invention.
Accompanying drawing is a method flow synoptic diagram of in fluidized-bed reactor, producing the stop bracket gasoline catalyzed conversion provided by the invention.Accompanying drawing adopts a fluidized-bed reactor, a revivifier and a separation column.
Raw oil after the preheating gets into riser tube 2 bottoms from pipeline 1, and preheating mixed with raw oil or gets into riser tubes 2 bottoms separately (or in the middle part of pipeline 15 entering riser tubes through pipeline 14 through pipeline 1 from the recycle stock of pipeline 13 afterwards; Or get into riser tube 2 from pipeline 1, pipeline 14 and pipeline 15 simultaneously).Contact with the regeneration rear catalyst that promotes from regenerator sloped tube 11 process preheating steam; Reactant flow gets into the settling vessel 5 that has the dense, fluidized bed bioreactor; Reaction oil gas is sent into follow-up separation column 12 through pipeline 6, separates the dry gas that obtains and draws through pipeline 16, separates the liquefied gas that obtains and draws through pipeline 17; Purpose product stop bracket gasoline (C5-160 ℃) is drawn through pipeline 18; Freshening cut (boiling range is 160-260 ℃) through cutting gets into riser tube 2 from freshening pipeline 13, and cutting back diesel oil distillate (boiling range is 260-350 ℃) is drawn through pipeline 19, and slurry oil is drawn through pipeline 20.Reclaimable catalyst gets into stripper 4; By from the entrained reaction oil gas of the steam stripped reclaimable catalyst of pipeline 3; Spent agent behind the stripping gets into revivifier 8 through inclined tube 7 to be generated, and oxygen-containing gas is introduced revivifier through pipeline 10, and reclaimable catalyst is coke burning regeneration under the effect of oxygen-containing gas; Regenerated flue gas is drawn revivifier through pipeline 9, and the pyritous regenerated catalyst returns the riser tube bottom cycle through regenerator sloped tube 11 and uses.
Following embodiment will further explain method provided by the invention, but therefore not make the present invention receive any restriction.
The character of employed raw oil and catalyzer is listed in table 1 and table 2 among the embodiment.Catalyzer in the table 2 is produced by China PetroChemical Corporation's Shandong catalyst plant.
Embodiment 1
The selected boiling range distillate of the present invention is adopted in the present embodiment explanation, in small-sized continuous fluid bed bioreactor, produces the situation of stop bracket gasoline.
The listed over point of table 1 uses catalyzer D greater than 165.6 ℃ the distillate B raw material as catalytic pyrolysis, carries out the distillate catalyzed conversion in the small-sized fluidized bed reaction of successive reaction regenerative operation in it and produces high-octane experiment.Distillate B mixes with the preheating high-temperature water vapor laggardly to go in the fluidized-bed reactor, is 500 ℃ in temperature of reaction, and reacting its top pressure is 0.2MPa, and weight hourly space velocity is 9h
-1, agent-oil ratio is 13, water vapor and the weight ratio of raw material are to contact with catalyzer under 0.11 the condition to carry out catalyzed conversion and produce stop bracket gasoline.Reaction product, steam and reclaimable catalyst separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst gets into stripper, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.Catalyzer behind the stripping enters into revivifier, contacts regeneration with the warm air that heated, and the catalyzer after the regeneration turns back to reactor cycles again and uses.Operational condition and product distribute and list in table 3.Can find out that by table 3 selected distillate transformation efficiency is higher, gasoline yield is up to 55.43% after the cracking, and RON (RON) is up to 94.9, and coke yield is also lower.
Comparative Examples 1
Compare with embodiment 1, raw oil is full range diesel oil, and other condition is basic identical.Operational condition, product distribute and list in table 3.Can find out that by table 3 for full boiling range diesel oil, the productive rate of its gasoline is merely 28.96%, octane value only 93.2, coke selectivity is also higher.
Embodiment 2
It is the situation of 180 ℃-245 ℃ cut production stop bracket gasoline that vacuum gas oil (VGO) freshening boiling range on medium-sized riser arrangement is adopted in the present embodiment explanation.
With the listed fraction A of table 1 is raw material, uses the catalyzer D in the table 2, on the medium-sized riser fluid catalytic cracking of successive reaction regenerative operation, carries out the experiment that the distillate freshening is produced stop bracket gasoline.Shown in accompanying drawing, promote steam in advance and get into by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 11 in the castering action lower edge riser tube that the promotes steam in advance accelerated motion that makes progress; The raw material A that also atomizes after the preheating enters into riser tube 2 through pipeline 14;, mix with the existing logistics of riser reactor, boiling range be 180 ℃-245 ℃ freshening cut through steam atomizing after pipeline 15 be injected in the riser tube; Mix with existing logistics in the riser reactor; Cracking reaction takes place in this distillate on the catalyzer that contains than the low-carbon (LC) amount, and upwards accelerated motion, and the oil gas of generation and the reclaimable catalyst of inactivation get into the cyclonic separator of settling vessel 5; The realization reclaimable catalyst separates with oil gas, and the oil gas after the separation gets into follow-up separation system 12 through gas pipeline 6.Catalyst fines after the separation returns settling vessel 5 by cyclone dip-leg.Reclaimable catalyst flows to stripping stage 4 in the settling vessel, contacts with steam from pipeline 3.The oil gas that stripping goes out from reclaimable catalyst gets into separation system through gas pipeline.Reclaimable catalyst inclined tube 7 behind the stripping gets into revivifier 8, and main air gets into revivifier through pipeline 10, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas is drawn the cigarette machine that gets into through pipeline 9.Test conditions, product distribute and list in table 4.
Can be found out that by table 4 yield of comparing present embodiment gasoline with Comparative Examples 2 improves 4.89 heavy %, the octane value of gasoline improves 1.8; Compare the yield high 3.93 heavy % of present embodiment gasoline with Comparative Examples 3, the octane value of gasoline is high by 1.7.
Comparative Examples 2
Compare with embodiment 2, this reaction is single-pass operation, and other condition is basic identical.Operational condition, product distribute and list in table 4.
Comparative Examples 3
Compare with embodiment 2, this reaction is a full range diesel oil freshening, and other condition is basic identical.Operational condition, product distribute and list in table 4.
Table 1
The raw material numbering |
A |
B |
C |
Type of feed |
VGO |
Mixing oil |
Diesel oil |
Density (20 ℃), kilogram/rice
3 |
907.4 |
852.7 |
904.4 |
Boiling range, ℃ |
|
|
|
Over point |
229.1 |
165.6 |
165.6 |
50% |
455.3 |
223.1 |
267.3 |
Final boiling point |
568.6 |
267.3 |
356.0 |
Table 2
Catalyzer |
D |
Chemical constitution, heavy % |
|
Al
2O
3 |
47.7 |
RE
2O
3 |
3.2 |
NaO |
0.27 |
Physical properties |
|
Specific surface area, m
2/g
|
110 |
Abrasion index, heavy % |
1.1 |
Micro-activity |
62 |
Table 3
|
Embodiment 1 |
Comparative Examples 1 |
The raw oil numbering |
B |
C |
Reaction conditions |
|
|
Temperature, ℃ |
460 |
460 |
Pressure, MPa |
0.2 |
0.2 |
Weight hourly space velocity, hour
-1 |
13 |
13 |
Agent-oil ratio |
9 |
9 |
The weight ratio of water vapor/raw material |
0.11 |
0.11 |
Product distributes, heavy % |
|
|
Dry gas |
1.43 |
2.98 |
Liquefied gas |
9.87 |
12.03 |
Gasoline |
55.43 |
28.96 |
Diesel oil |
26.35 |
37.91 |
Slurry oil |
3.46 |
12.55 |
Coke |
3.21 |
5.32 |
Loss |
0.25 |
0.25 |
The gasoline main character |
|
|
Aromaticity content, heavy % |
59.32 |
43.80 |
RON |
94.9 |
93.2 |
Table 4
|
Embodiment 2 |
Comparative Examples 2 |
Comparative Examples 3 |
The raw oil numbering |
A |
A |
A |
Reaction conditions |
|
|
|
Temperature, ℃ |
550 |
550 |
550 |
Pressure, MPa |
0.31 |
0.31 |
0.31 |
Weight hourly space velocity, hour-1 |
6 |
6 |
6 |
Agent-oil ratio |
6 |
6 |
6 |
Water vapor/raw material weight ratio |
0.18 |
0.18 |
0.18 |
Product distributes, heavy % |
|
|
|
Dry gas |
3.21 |
3.01 |
3.15 |
Liquefied gas |
14.12 |
13.38 |
14.56 |
Gasoline |
46.98 |
42.09 |
43.05 |
Diesel oil |
24.73 |
30.76 |
24.78 |
Slurry oil |
3.23 |
3.06 |
5.81 |
Coke |
7.43 |
7.40 |
8.35 |
Loss |
0.30 |
0.30 |
0.30 |
The gasoline main character |
|
|
|
Aromaticity content, heavy % |
21.53 |
17.22 |
19.52 |
RON |
93.0 |
91.2 |
91.3 |