CN103540338A - Catalytic cracking process - Google Patents
Catalytic cracking process Download PDFInfo
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- CN103540338A CN103540338A CN201210244840.3A CN201210244840A CN103540338A CN 103540338 A CN103540338 A CN 103540338A CN 201210244840 A CN201210244840 A CN 201210244840A CN 103540338 A CN103540338 A CN 103540338A
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Abstract
The invention discloses a catalytic cracking process, aiming at overcoming the defects such as high dry gas yield and low light oil yield in an existing riser catalytic cracking device. The process comprises the following steps: feeding raw material oil into the lower part of a riser reactor; enabling the raw material to be in contact with a regenerated catalyst from a regenerator to react; separating the reacted oil gas from the catalyst to be generated; feeding the separated reaction oil gas into a fractionating tower; feeding the separated catalyst to be generated into a stripping section of a settler; feeding dry gas into the stripping section of the settler to contact with the catalyst to be generated for reaction; feeding the reacted oil gas into the fractionating tower; carrying out steam stripping on the catalyst to be generated and then feeding into the regenerator to regenerate; and recycling the regenerated catalyst. By using the process, the dry gas yield can be reduced by 0.3-1.5 percent, and the light oil yield can be increased by 0.3-1.4 percent.
Description
Technical field
The invention belongs to the catalytic cracking field of hydrocarbon ils in the situation that not there is not hydrogen, particularly a kind of reduction dry gas yied, improves the catalytic cracking process of light oil yield.
Background technology
Not only will focus on environment protection, the maximization of economic benefit also should be paid close attention to.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 riser fluid catalytic cracking the shortcomings such as the higher and light oil yield of dry gas yied is low, and a kind of reduction device dry gas yied is provided, improve the new catalytic cracking process of light oil yield simultaneously.
The invention provides a kind of catalytic cracking process, it is characterized in that comprising the steps:
1) stock oil enters riser reactor bottom, and with the regenerated catalyst contact reacts from revivifier, reacted oil gas is separated with reclaimable catalyst, and isolated reaction oil gas enters separation column, and isolated reclaimable catalyst enters settling vessel stripping stage;
2) dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts, and reacted oil gas enters separation column, and reclaimable catalyst enters revivifier and regenerates after stripping, and the regenerated catalyst after regeneration turns back to step 1).
Reacted oil gas of the present invention is separated with reclaimable catalyst, and isolated reaction oil gas enters separation column after further isolating catalyst fines.
Dry gas of the present invention enters settling vessel stripping stage and reclaimable catalyst contact reacts, and dry gas is for this device is self-produced or from other catalytic cracking or on-catalytic cracking unit.
Reaction conditions when dry gas of the present invention enters settling vessel stripping stage and reclaimable catalyst contact reacts is: temperature of reaction is 440～560 ℃, preferably 450～550 ℃, is preferably 460～540 ℃; Dry gas weight hourly space velocity is 0.01～1.0h
-1, 0.03～0.8h preferably
-1, be preferably 0.05～0.5h
-1; Reaction absolute pressure is 0.15～0.40MPa, and preferably 0.20～0.36MPa, is preferably 0.22～0.35MPa.
Riser reactor temperature of reaction of the present invention 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 1.2～4.0 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 4～15, be preferably 5～13; Reaction absolute pressure is 0.15～0.40MPa, and preferably 0.20～0.36MPa, is preferably 0.22～0.35MPa.
The regeneration temperature of revivifier of the present invention is 650～750 ℃, and the carbon content of reclaimable catalyst after regeneration in-situ regeneration is 0.02～0.2 % by weight, and micro-activity is generally 55～70.
The present invention compares with existing single riser catalytic cracking technique, and existing catalytic cracking process is improved.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 settling vessel stripping stage and reclaimable catalyst contact reacts by the dry gas that produced, reaction generation gasoline and the diesel oil such as superimposed, the alkylation mainly occurring by ethene in dry gas, cyclisation, aromizing and hydrogen transference.Through above reaction process, can obviously reduce dry gas yied, improve light oil yield.Vapour, diesel oil character are substantially constant.Use the present invention can make the dry gas yied of single riser fluid catalytic cracking decline 0.3～1.5 percentage point, light oil yield (gasoline+diesel oil) improves 0.3～1.4 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 single riser catalytic cracking test device, test, riser tube charging is for mixing heavy oil, and main character is listed in table 1, and treatment capacity is 30 kg/day; Test used catalyst is RSC-2006 industry poiser, and equilibrium catalyst micro-activity is 60, and carbon content is 0.03w%.The main operational condition of catalytic cracking test device, product distribute and list in table 2.
Embodiment 2 (comparative example)
Press embodiment 1, difference is that riser tube temperature of reaction is 510 ℃, and main operational condition, product distribute and list in table 2.
Embodiment 3 (comparative example)
Press embodiment 1, difference is that riser tube temperature of reaction is 520 ℃, 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 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 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 settling vessel stripping stage, and main operational condition, product distribute and list in table 3.
The main character of table 1 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 | RSC-2006 | RSC-2006 | RSC-2006 |
| Main operational condition | |||
| Riser tube temperature of reaction/℃ | 500 | 510 | 520 |
| Reaction pressure (gauge pressure)/MPa | 0.18 | 0.18 | 0.18 |
| Agent-oil ratio | 6.0 | 6.6 | 7.1 |
| Reaction times/s | 2.96 | 2.88 | 2.83 |
| Product distribution/% by weight | |||
| Dry gas | 3.51 | 3.73 | 4.06 |
| Liquefied gas | 11.12 | 13.03 | 14.58 |
| Gasoline | 39.25 | 40.89 | 41.33 |
| Diesel oil | 32.92 | 28.93 | 26.49 |
| Slurry oil | 5.00 | 5.00 | 5.00 |
| Coke | 7.70 | 7.92 | 8.04 |
| Loss | 0.50 | 0.50 | 0.50 |
| Add up to | 100 | 100 | 100 |
| Light oil yield (gasoline+diesel oil) | 72.17 | 69.82 | 67.82 |
The main operational condition of table 3 and product distribute
| Project | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Catalyzer | RSC-2006 | RSC-2006 | RSC-2006 |
| Main operational condition | |||
| Riser tube temperature of reaction/℃ | 500 | 510 | 520 |
| Reaction pressure (gauge pressure)/MPa | 0.18 | 0.18 | 0.18 |
| Agent-oil ratio | 6.0 | 6.6 | 7.1 |
| Reaction times/s | 2.96 | 2.88 | 2.83 |
| Settling vessel stripping stage temperature/℃ | 489 | 500 | 506 |
| Enter settling vessel stripping stage dry gas weight hourly space velocity/h -1 | 0.05 | 0.1 | 0.2 |
| Product distribution/% by weight | |||
| Dry gas | 2.88 | 3.01 | 3.25 |
| Liquefied gas | 11.21 | 13.18 | 14.63 |
| Gasoline | 39.61 | 41.26 | 41.96 |
| Diesel oil | 33.09 | 29.10 | 26.60 |
| Slurry oil | 5.00 | 5.00 | 5.00 |
| Coke | 7.71 | 7.95 | 8.06 |
| Loss | 0.50 | 0.50 | 0.50 |
| Add up to | 100 | 100 | 100 |
| Light oil yield (gasoline+diesel oil) | 72.70 | 70.36 | 68.56 |
Claims (11)
1. a catalytic cracking process, is characterized in that comprising the steps:
1) stock oil enters riser reactor bottom, and with the regenerated catalyst contact reacts from revivifier, reacted oil gas is separated with reclaimable catalyst, and isolated reaction oil gas enters separation column, and isolated reclaimable catalyst enters settling vessel stripping stage;
2) dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts, and reacted oil gas enters separation column, and reclaimable catalyst enters revivifier and regenerates after stripping, and the regenerated catalyst after regeneration turns back to step 1).
2. catalytic cracking process according to claim 1, is characterized in that: described reacted oil gas is separated with reclaimable catalyst, and isolated reaction oil gas enters separation column after further isolating catalyst fines.
3. catalytic cracking process according to claim 1, is characterized in that: described dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts, and dry gas is for this device is self-produced or from other catalytic cracking or on-catalytic cracking unit.
4. catalytic cracking process according to claim 1, is characterized in that: reaction conditions when described dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts is: temperature of reaction is 440～560 ℃, and dry gas weight hourly space velocity is 0.01～1.0h
-1, reaction absolute pressure is 0.15～0.40MPa.
5. catalytic cracking process according to claim 4, is characterized in that: temperature of reaction when described dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts is 450～550 ℃.
6. catalytic cracking process according to claim 5, is characterized in that: temperature of reaction when described dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts is 460～540 ℃.
7. according to the catalytic cracking process described in claim 4 or 5, it is characterized in that: the absolute pressure of reacting when described dry gas enters settling vessel stripping stage with reclaimable catalyst contact reacts is 0.20～0.36MPa, and dry gas weight hourly space velocity is 0.03～0.8h
-1.
8. catalytic cracking process according to claim 7, is characterized in that: dry gas weight hourly space velocity when described dry gas enters settling vessel stripping stage and reclaimable catalyst contact reacts is 0.05～0.5h
-1, reaction absolute pressure is 0.22～0.35MPa.
9. catalytic cracking process according to claim 1, is characterized in that: described 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.
10. catalytic cracking process according to claim 9, is characterized in that: described 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 4～15, and reaction absolute pressure is 0.20～0.36MPa.
11. catalytic cracking process according to claim 1, is characterized in that: the regeneration temperature of described revivifier is 650～750 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210244840.3A CN103540338A (en) | 2012-07-09 | 2012-07-09 | Catalytic cracking process |
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|---|---|---|---|
| CN201210244840.3A CN103540338A (en) | 2012-07-09 | 2012-07-09 | Catalytic cracking process |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401742A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Method and apparatus for catalytic upgrading poor gasoline |
| CN1710029A (en) * | 2005-07-01 | 2005-12-21 | 中国石油化工集团公司 | Catalytic cracking method and apparatus |
| CN102268290A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking method and device |
-
2012
- 2012-07-09 CN CN201210244840.3A patent/CN103540338A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401742A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Method and apparatus for catalytic upgrading poor gasoline |
| CN1710029A (en) * | 2005-07-01 | 2005-12-21 | 中国石油化工集团公司 | Catalytic cracking method and apparatus |
| CN102268290A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking method and device |
Non-Patent Citations (1)
| Title |
|---|
| 陈祥 等: "催化裂化干气中乙烯制汽油工业实验", 《广州化工》 * |
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Application publication date: 20140129 |