CN103540337A - Catalytic cracking method - Google Patents
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- CN103540337A CN103540337A CN201210244837.1A CN201210244837A CN103540337A CN 103540337 A CN103540337 A CN 103540337A CN 201210244837 A CN201210244837 A CN 201210244837A CN 103540337 A CN103540337 A CN 103540337A
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Abstract
The invention discloses a catalytic cracking method for overcoming the defects such as relatively high dry gas yield, low light oil yield and the like in the traditional double-riser catalytic cracking device. The method comprises the steps that raw oil enters the lower part of a heavy oil riser reactor of a double-riser catalytic cracking device, crude gasoline is subjected to contact reaction with a catalyst from a regenerator after entering the lower part of a gasoline riser reactor of the double-riser catalytic cracking device, and the reacted gasoline spent catalyst enters a stripping section of an auxiliary settler; dry gas is subjected to contact reaction with the spent catalyst after entering the stripping section of the auxiliary settler, the reacted oil gas enters an auxiliary fractionating tower, and after being stripped, part of gasoline spent catalyst enters the regenerator so as to be regenerated, and the other part of gasoline spent catalyst enters a pre-rising mixer so as to be mixed with a regenerant from the regenerator. By using the method disclosed by the invention, the yield of the dry gas can be reduced by 0.3-1.5%, and the yield of the light oil can be increased by 0.3-1.3%.
Description
Technical field
The invention belongs in the situation that not there is not hydrogen, the catalytic cracking field of hydrocarbon ils, particularly a kind of reduction dry gas yied, improves the catalyst cracking method of light oil yield.
Background technology
When focusing on environment protection, the maximization of economic benefit is the target that enterprise is pursued forever.And low dry gas yied, high light receipts are the important means that catalytic cracking technology is increased economic efficiency always.In recent years, domestic each research institution has carried out fruitful research being devoted to improve aspect the distribution of catalytic cracking product, and the technology of exploitation mainly contains following several:
The US of Uop Inc. 5451313 is disclosed, and " this new design has been invented in nineteen ninety-five by X design ”， Uop Inc., its objective is rising agent oil ratio, improves product and distributes.Be characterized in being provided with a catalyst mix device between reactor and revivifier, spent agent mixes in mixing tank with regenerator, and part mixture flows into riser tube and raw material contact reacts, and remaining mixture flows into revivifier and regenerates.The benefit of this structure is the mixture temperature that enters riser tube than next low of revivifier, and catalyst recirculation amount is increased, and agent-oil ratio improves, so thermal response minimizings, catalyzed reaction increase, coke and dry gas yied reduce, gasoline yield increase.But it is very low that this design shortcoming is exactly spent agent activity in mixed catalyst, makes the activity of mixture on the low side, is unfavorable for the cracking of stock oil.
The IsoCat technique of Petrobras company (US 6059958), is characterized in being divided into two strands through the cooling catalyzer of external warmer, and one returns to regenerator bed, another strand with enter riser tube after hot regenerated catalyst mixes and react with stock oil.Obviously, the temperature of mixed regeneration catalyzer is lower than the temperature of conventional regenerated catalyst.Similar with " X design " reason of Uop Inc., IsoCat technique can reduce coke and dry gas yied, and two strands of catalyzer of IsoCat technique are regenerated catalyst, and the activity of mixture is higher, is more conducive to catalyzed reaction.But this technique implements comparatively complicated, and mixed catalyst difficult control of temperature.
The disclosed regenerator sloped tube catalyzer of CN 1288933 cooling technology, this method is exactly directly at regenerator sloped tube, a cooling water jecket to be set outward, by water coolant, the regenerated catalyst temperature that enters riser reactor is lowered.Although this method has obtained good effect on pilot plant, dry gas and coke yield are significantly declined, bring very large difficulty in industrial practice the control of temperature of reaction, that is to say that this method seems simply, put into practice difficulty larger.
China University Of Petroleum Beijing has proposed Novel multi association control heavy oil MZCC catalytic cracking technology (< < oil Refining Technologies and engineering > > the 12nd phase in 2008), MZCC technology be take the heat that mixes of optimizing heavy oil and regenerator and is promoted the cracking of hydro carbons macromole, reduces dry gas and coke is technique basis, has proposed the strong back-mixing of charging, the propelling of reaction advection, the ultrafast separation of product and chemical steam stripped subregion Collaborative Control new concept.This technology is intended a newly-increased root regeneration inclined tube and air-lift unit pipe, and on this newly-increased regenerator sloped tube, catalyst cooler is set, cooled catalyzer mixes with the thermocatalyst that former regenerator sloped tube comes, after mixing, regenerator and the raw material of lesser temps carry out contact reacts, this technology can reduce finish mixing temperature, and rising agent oil ratio is improved product and distributed, but this technology regenerator cooling measure is slightly aobvious complicated, need set up equipment more.
The double lift pipe catalytic cracking technique that CN1710029 is disclosed, this technology is developed by Luoyang Petrochemical engineering corporation, adopt double lifting leg and set up petrol sediment bulb and secondary separation column, the lower gasoline rising pipe reclaimable catalyst of part relative temperature is introduced to stock oil riser tube catalyzer pre-lift mixing tank simultaneously, after mixing with high temperature regeneration agent, enter stock oil riser tube, so both reduced the finish Contact Temperature of stock oil riser tube, take full advantage of again the remaining activity of gasoline rising pipe reclaimable catalyst, improve agent-oil ratio and the product selectivity of stock oil riser catalytic cracking, reduce dry gas and coke yield, improve propene yield and Propylene Selectivity.But this technology is in actual industrial implementation process, although reached gasoline upgrading, propylene enhancing and improved the object that product distributes, but because the dry gas that gasoline upgrading brings is more, cause the total dry gas yied of device still higher, light oil yield is relatively low, therefore still need to carry out technological improvement, the overall benefit of device is further improved.
Summary of the invention
The present invention be directed in existing Double-lifted pipe catalytic cracking device the shortcomings such as the higher and light oil yield of dry gas yied is low, and a kind of reduction dry gas yied is provided, improve the new catalyst cracking method of light oil yield simultaneously.
The invention provides a kind of catalyst cracking method, it is characterized in that comprising the steps:
1) stock oil enters Double-lifted pipe catalytic cracking device heavy oil riser reactor bottom, with the catalyzer contact reacts from pre-lift mixing tank, reacted oil gas is separated with reclaimable catalyst, isolated reaction oil gas enters main fractionating tower, and isolated reclaimable catalyst enters main settling vessel stripping stage and after stripping, enters revivifier regeneration;
2) raw gasline enters Double-lifted pipe catalytic cracking device gasoline rising pipe reactor lower part, with the catalyzer contact reacts from revivifier, reacted oil gas is separated with reclaimable catalyst, isolated reaction oil gas enters secondary separation column, and isolated reclaimable catalyst enters secondary settling vessel stripping stage;
3) dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, reacted oil gas enters secondary separation column, reclaimable catalyst enters revivifier regeneration through stripping rear portion, catalyst recirculation after regeneration is used, another part enters pre-lift mixing tank to be mixed with the regenerator from revivifier, and mixed catalyzer turns back to step 1) mix with stock oil.
Described reacted oil gas is separated with reclaimable catalyst, and isolated reaction oil gas further isolates that catalyst fines is laggard enters main fractionating tower or secondary separation column.
Described dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, and dry gas is for this device is self-produced or from other catalytic cracking or on-catalytic cracking unit.
Described a kind of catalyst cracking method, dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, and temperature of reaction is 300～600 ℃, preferably 350～580 ℃, is preferably 380～560 ℃; Dry gas weight hourly space velocity is 0.03～1.5h
-1, 0.06～1.0h preferably
-1, be preferably 0.1～0.8h
-1; Reaction absolute pressure is 0.15～0.40MPa, and preferably 0.20～0.36MPa, is preferably 0.22～0.35MPa.
Described heavy oil riser reactor temperature of reaction is 450～560 ℃, preferably 460～540 ℃, is preferably 470～530 ℃; Reaction times is 0.5～5 second, preferably 1.0～4.5 seconds, is preferably 1.5～4.0 seconds; Agent weight of oil is 3～20 than (catalyst recirculation amount and inlet amount weight ratio, catalyst recirculation amount is by leg outlet internal circulating load), preferably 5～18, be preferably 7～15; Reaction absolute pressure is 0.15～0.40MPa, and preferably 0.20～0.36MPa, is preferably 0.22～0.35MPa; Stock oil riser reactor bottom pre-lift mixer temperature is 550～700 ℃, preferably 580～670 ℃, is preferably 590～660 ℃; The regeneration temperature of revivifier is 650～750 ℃.The regenerated catalyst of reclaimable catalyst after regeneration in-situ regeneration, its carbon content is generally 0.02～0.2 % by weight, and micro-activity is generally 55～70.
Described gasoline rising pipe reactor reaction temperature is 320～630 ℃, preferably 350～600 ℃, is preferably 370～580 ℃; Reaction times is 0.5～5 second, preferably 1.0～4.5 seconds, is preferably 1.5～4.0 seconds; Agent weight of oil is 3～20 than (catalyst recirculation amount and inlet amount weight ratio, catalyst recirculation amount is by leg outlet internal circulating load), preferably 4～18, be preferably 5～15; Reaction absolute pressure is 0.15～0.40MPa, and preferably 0.20～0.36MPa, is preferably 0.22～0.35MPa; Described gasoline rising pipe reactor feed at least contains a kind of in the petroleum naphtha of catalytically cracked gasoline, catalytic cracking gasoline, pressure gasoline, cracking ethylene preparation gasoline, coker gasoline, straight-run spirit and above gasoline or heavy petrol.
The present invention compares with existing double lift pipe catalytic cracking method, is a kind of improvement to existing double lift pipe catalytic cracking method.In catalytic cracking production, the hydrogen massfraction that is worth lower by product-dry gas approaches 25%, therefore, and for the catalytic cracking reaction of hydrogen self-equilibrating, reducing dry gas yied is the effective rate of utilization that improves hydrogen, carbon in raw material, obtains the key of higher yield of light oil and liquid yield.
The present invention introduces secondary settling vessel stripping stage and gasoline spent agent contact reacts by the dry gas having produced, and the reactions such as superimposed, the alkylation mainly occurring by ethene in dry gas, cyclisation, aromizing and hydrogen transference generate gasoline and diesel oil.Through above reaction process, can obviously reduce dry gas yied, improve light oil yield.Vapour, diesel oil character are substantially constant.Use the inventive method can make the dry gas yied of Double-lifted pipe catalytic cracking device decline 0.3～1.5 percentage point; Light oil yield (gasoline+diesel oil) improves 0.3～1.3 percentage point.
Utilize embodiment to be further detailed the present invention below, but do not limit the scope of the invention.
Embodiment
Embodiment 1 (comparative example)
On double lift pipe catalytic cracking testing apparatus, test, the charging of heavy oil riser tube is for mixing heavy oil, and main character is listed in table 1, and treatment capacity is 30 kg/day; Gasoline rising pipe charging is the self-produced gasoline of device, and treatment capacity is 12 kg/day.Test used catalyst is MLC-500 industry poiser, and equilibrium catalyst micro-activity is 62, and carbon content is 0.05w%.The main operational condition of double lift pipe catalytic cracking testing apparatus, product distribute and list in table 2.
Embodiment 2 (comparative example)
Press embodiment 1, difference is that gasoline rising pipe temperature of reaction is 520 ℃, and main operational condition, product distribute and list in table 2.
Embodiment 3 (comparative example)
Press embodiment 1, difference is that gasoline rising pipe temperature of reaction is 500 ℃, and main operational condition, product distribute and list in table 2.
Embodiment 4
Press embodiment 1, difference is that the self-produced dry gas of device enters secondary settling vessel stripping stage, and main operational condition, product distribute and list in table 3.
Embodiment 5
Press embodiment 2, difference is that the self-produced dry gas of device enters secondary settling vessel stripping stage, and main operational condition, product distribute and list in table 3.
Embodiment 6
Press embodiment 3, difference is that the self-produced dry gas of device enters secondary settling vessel stripping stage, and main operational condition, product distribute and list in table 3.
The main character of table 1 heavy oil riser reactor charging
| Project | Embodiment 1～6 |
| Stock oil title | Mix heavy oil |
| Density (20 ℃)/kg.m -3 | 923.6 |
| Carbon residue/% | 3.50 |
| Molecular weight | 450 |
| Boiling range/℃ | |
| IBP | 320 |
| 10％ | 375 |
| 30％ | / |
| 50％ | 450 |
| 70％ | / |
| 90％ | 589 |
| C/ % by weight | 86.65 |
| H/ % by weight | 12.25 |
| S/ % by weight | 0.65 |
| N/ % by weight | 0.14 |
| Group composition/% by weight | |
| Stable hydrocarbon | 54.26 |
| Aromatic hydrocarbons | 32.10 |
| Colloid+bituminous matter | 13.64 |
| Metal content/μ g.g -1 | |
| Ni | 4.4 |
| V | 9.0 |
| Fe | 1.7 |
| Na | 1.5 |
The main operational condition of table 2 and product distribute
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Catalyzer | MLC-500 | MLC-500 | MLC-500 |
| Main operational condition | |||
| Outlet temperature of riser/℃ * | 520/550 | 520/520 | 520/500 |
| Reaction pressure (gauge pressure) */MPa | 0.20/0.20 | 0.20/0.20 | 0.20/0.20 |
| Agent-oil ratio * | 9.8/12.1 | 9.8/10.2 | 9.8/8.0 |
| Reaction times */s | 2.92/3.01 | 2.90/3.05 | 2.96/3.10 |
| Product distribution/% by weight | |||
| Dry gas | 4.29 | 4.08 | 3.95 |
| Liquefied gas | 24.25 | 22.87 | 21.54 |
| Gasoline | 31.13 | 32.64 | 34.09 |
| Diesel oil | 26.97 | 27.14 | 27.23 |
| Slurry oil | 5.00 | 5.00 | 5.00 |
| Coke | 7.86 | 7.77 | 7.69 |
| Loss | 0.50 | 0.50 | 0.50 |
| Add up to | 100 | 100 | 100 |
| Light oil yield (gasoline+diesel oil) | 58.10 | 59.78 | 61.32 |
* notes/front oil riser the reaction parameter of attaching most importance to ,/be gasoline rising pipe reaction parameter afterwards.
The main operational condition of table 3 and product distribute
* notes/front oil riser the reaction parameter of attaching most importance to ,/be gasoline rising pipe reaction parameter afterwards.
Claims (12)
1. a catalyst cracking method, is characterized in that comprising the steps:
1) stock oil enters Double-lifted pipe catalytic cracking device heavy oil riser reactor bottom, with the catalyzer contact reacts from pre-lift mixing tank, reacted oil gas is separated with reclaimable catalyst, isolated reaction oil gas enters main fractionating tower, and isolated reclaimable catalyst enters main settling vessel stripping stage and after stripping, enters revivifier regeneration;
2) raw gasline enters Double-lifted pipe catalytic cracking device gasoline rising pipe reactor lower part, with the catalyzer contact reacts from revivifier, reacted oil gas is separated with reclaimable catalyst, isolated reaction oil gas enters secondary separation column, and isolated reclaimable catalyst enters secondary settling vessel stripping stage;
3) dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, reacted oil gas enters secondary separation column, reclaimable catalyst enters revivifier regeneration through stripping rear portion, catalyst recirculation after regeneration is used, another part enters pre-lift mixing tank to be mixed with the regenerator from revivifier, and mixed catalyzer turns back to step 1) mix with stock oil.
2. catalyst cracking method according to claim 1, is characterized in that: described reacted oil gas is separated with reclaimable catalyst, and isolated reaction oil gas further isolates that catalyst fines is laggard enters main fractionating tower or secondary separation column.
3. catalyst cracking method according to claim 1, is characterized in that: described dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, and dry gas is for this device is self-produced or from other catalytic cracking or on-catalytic cracking unit.
4. catalyst cracking method according to claim 1, is characterized in that: described dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, and temperature of reaction is 300～600 ℃, and dry gas weight hourly space velocity is 0.03～1.5h
-1, reaction absolute pressure is 0.15～0.40MPa.
5. catalyst cracking method according to claim 4, is characterized in that: described dry gas enters secondary settling vessel stripping stage and gasoline spent agent contact reacts, and temperature of reaction is 350～580 ℃, and dry gas weight hourly space velocity is 0.06～1.0h
-1, reaction absolute pressure is 0.20～0.36MPa.
6. catalyst cracking method according to claim 1, is characterized in that: described heavy oil riser reactor temperature of reaction is 450～560 ℃, and the reaction times is 0.5～5 second, and agent weight of oil ratio is 3～20, and reaction absolute pressure is 0.15～0.40MPa.
7. catalyst cracking method according to claim 1, is characterized in that: described stock oil riser reactor bottom pre-lift mixer temperature is 550～700 ℃.
8. catalyst cracking method according to claim 7, is characterized in that: described stock oil riser reactor bottom pre-lift mixer temperature is 580～670 ℃.
9. catalyst cracking method according to claim 6, is characterized in that: described heavy oil riser reactor temperature of reaction is 460～540 ℃, and the reaction times is 1.0～4.5 seconds, and agent weight of oil ratio is 5～18, and reaction absolute pressure is 0.20～0.36MPa.
10. catalyst cracking method according to claim 1, is characterized in that: the regeneration temperature of described revivifier is 650～750 ℃.
11. catalyst cracking methods according to claim 1, is characterized in that: described gasoline rising pipe reactor reaction temperature is 320～630 ℃, and the reaction times is 0.5～5 second, and agent weight of oil ratio is 3～20, and reaction absolute pressure is 0.15～0.40MPa.
12. catalyst cracking methods according to claim 1, is characterized in that: described gasoline rising pipe reactor reaction temperature is 350～600 ℃, and the reaction times is 1.0～4.5 seconds, and agent weight of oil ratio is 4～18, and reaction absolute pressure is 0.20～0.36MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974787A (en) * | 2014-04-08 | 2015-10-14 | 中石化洛阳工程有限公司 | Catalytic cracking method of increasing gasoline yield |
| CN105441114A (en) * | 2014-09-12 | 2016-03-30 | 中石化洛阳工程有限公司 | Catalytic cracking apparatus |
| CN111116775A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Process and apparatus for preparing low viscosity poly α -olefins |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974787A (en) * | 2014-04-08 | 2015-10-14 | 中石化洛阳工程有限公司 | Catalytic cracking method of increasing gasoline yield |
| CN104974787B (en) * | 2014-04-08 | 2018-04-20 | 中石化洛阳工程有限公司 | A kind of catalyst cracking method of fecund gasoline |
| CN105441114A (en) * | 2014-09-12 | 2016-03-30 | 中石化洛阳工程有限公司 | Catalytic cracking apparatus |
| CN105441114B (en) * | 2014-09-12 | 2017-05-24 | 中石化洛阳工程有限公司 | Catalytic cracking apparatus |
| CN111116775A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Process and apparatus for preparing low viscosity poly α -olefins |
| CN111116775B (en) * | 2018-10-30 | 2022-10-21 | 中国石油化工股份有限公司 | Process and apparatus for producing low viscosity polyalphaolefin |
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Application publication date: 20140129 |