CN1307086A - Method for catalytic cracking residue in supercritical solvent - Google Patents
Method for catalytic cracking residue in supercritical solvent Download PDFInfo
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- CN1307086A CN1307086A CN 00110054 CN00110054A CN1307086A CN 1307086 A CN1307086 A CN 1307086A CN 00110054 CN00110054 CN 00110054 CN 00110054 A CN00110054 A CN 00110054A CN 1307086 A CN1307086 A CN 1307086A
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Abstract
The catalytic cracking process of residue in supercritical condition with gasoline fraction, diesel oil fraction, benzene, dimethyl benzene, etc. as supercritical solvent can obtain very low final gas yield, high fraction oil yield, less coking on catalyst and long term catalyst activity and stability.
Description
The present invention relates to a kind of catalytic cracking technology, mainly is the treatment process that contains residual oil or heavy distillate raw material, especially contains the method for the catalytic cracking of residual oil raw material.
Fluid catalytic cracking is important secondary processing means, it with stock oil be in fluid catalyst and carry out contact reacts, finish mixes, speed of response is fast, the yield of light oil height is good in economic efficiency.Yet existing fluid catalytic cracking technology also has weak point: because catalyzer is in fluidized state, accelerate equipment attrition and catalyst breakage; Catalyst deactivation is exceedingly fast, and needs frequent regeneration, causes environmental pollutions such as energy dissipation and flue dust, noise; Owing to be subjected to the restriction of stock oil carbon residue and two indexs of heavy metal, existing fluid catalytic cracking technology can not be handled the mink cell focus of all kinds, particularly vacuum residuum in addition; In addition, residual oil can not be vaporized under the catalytic cracking condition of prior art fully, and reaction is to carry out under gas-liquid-solid three-phase condition, has a strong impact on product and distributes, and gas yield is raise, and coke yield raises significantly, and thermal equilibrium is destroyed.Balancing the too much coke of generation with the method for heat-obtaining, be equivalent to the liquid petroleum of preciousness is used for taking place steam, is a kind of covert waste of petroleum resources.
For improving the shortcoming of heavy oil fluid catalytic cracking, Chinese patent CN1107874A has proposed a kind of new heavy oil fluid catalytic cracking method.Concrete scheme is that mink cell focus is mixed by 1: 20 with atlapulgite or catalytic cracking spent catalyst, and the high-temperature water vapor with 450～550 ℃ in reactor is handled.Because the existence of a large amount of water vapour, the oil gas differential pressure drop of mink cell focus is low to moderate is equivalent to the underpressure distillation state, in about 100 minutes of reaction times, reaction finishes the back and removes residue.The advantage of this method is that the residual oil dividing potential drop is very low, can fully vaporize, but weak point is a long reaction time that transformation efficiency is low, periodical operation, and treatment capacity is little, is not suitable for scale operation, and the catalyzer of coking can not be regenerated.
Supercutical fluid is meant and is compressed and is heated to emergent pressure Pc and the above fluid of critical temperature Tc.It has the density of similar liquids, and dissolving power and liquid phase are worked as; Have the viscosity and the spread coefficient of similar gas simultaneously, this will improve the rate of mass transfer of fluidic movement velocity and sepn process.The most important character of supercutical fluid is that compressibility is very big, and the less variation of temperature or pressure can cause the bigger variation of supercritical flow volume density, thereby changes its dissolving power.Supercutical fluid makes the chemical reaction that carries out in supercritical solvent have the rate of diffusion of raising, increase reactants dissolved degree, prolongation solid catalyst life-span, reduce advantages such as temperature of reaction, raising speed of reaction because it has the solvent property of uniqueness.By literature search, there is no catalytically cracked materials such as relevant heavy distillate or residual oil carry out catalytic cracking in supercritical solvent document and patent report both at home and abroad.
The objective of the invention is to utilize supercutical fluid can improve the characteristics of heterogeneous catalytic reaction; supercritical technology is combined with existing catalytic cracking technology; provide a kind of in the presence of supercritical solvent residual oil or the catalyst cracking method of heavy distillate; make full use of petroleum resources; improve the light-end products yield, strengthen environmental protection simplifies the operation; reduce cost, improve the economic and social benefits.
Content of the present invention:
After catalytically cracked material and solvent, be forced into the emergent pressure or the supercritical pressure of described solvent, be heated to the critical temperature or the supercritical temperature of described solvent, entering reactor then contacts with catalytic cracking catalyst, carry out the catalytic cracking reaction under the supercritical state, the final reaction product enters separation system to be separated.
Described catalytically cracked material is the raw material that contains residual oil or heavy distillate, can be the long residuum of full cut and one or more mixtures in the vacuum residuum, also heavy distillate mixes one or both of long residuum or vacuum residuum, also 100% heavy distillate.In addition, the organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal also can be used as raw material.Taking all factors into consideration from the angle of economy, is that raw material is best with full cut vacuum residuum.
Described solvent is to be selected from benzene,toluene,xylene, pentamethylene, cyclohexane, low molecule alkane (one or more in C5～C8), gasoline fraction, the diesel oil distillate; Taking all factors into consideration, better is to be selected from toluene, dimethylbenzene, gasoline fraction, the diesel oil distillate one or more; Preferably be selected from gasoline fraction, the diesel oil distillate one or both; The boiling spread of described gasoline fraction solvent is 35～200 ℃, and the boiling spread of described diesel oil distillate solvent is 200～300 ℃.
Catalyst system therefor is conventional catalytic cracking catalyst, generally can adopt the zeolite molecular sieve that contains 5～15w%, and all the other are the catalytic cracking catalyst of pure aluminium silicate carrier.
Described reactor types can be selected according to actual needs, for example can select the anti-device of fixed bed, also can select expanded bed and suspended-bed reactor etc.Take all factors into consideration from the economy equal angles, better with the form of expanded bed and fixed bed, fixed-bed reactor are best.
Described solvent is called the molten slag ratio with the weight ratio of residual oil, is generally 0.1～6.0, is preferably 1.0～4.0, is preferably 2.0～3.0; Described temperature of reaction is generally 380～500 ℃, is preferably 400～480 ℃, is preferably 420～460 ℃; Described reaction pressure is generally 3～15MPa, is preferably 4～13MPa, is preferably 5～11MPa; The weight space velocity of described reaction is generally 15～80h
-1, be preferably 30～60h
-1, be preferably 40～50h
-1
The sepn process of described reaction product can enter flashing tower for: reaction product after decompression, top of tower is drawn cracked gas, and the reaction product of drawing at the bottom of the flash distillation Tata enters fractionating system after decompression.Isolate light ends oil, heavy distillate and cracking residual oil in fractionating system, solvent also can be in these whole recovery.Recovered solvent is direct removal system both, also can recycle.Heavy distillate both can all go out device, also can a part go out device, another part can be used as recycle stock to be mixed with fresh feed, cracking circulates, also can all circulate as recycle stock, (ratio of recycle stock and fresh feed weight of oil is generally between 0～0.5 recycle ratio, is preferably between 0.2～0.4.Because the superiority that present method is outstanding, prevented the degree of depth condensation reaction of heavy raw oil, most shallow degree condensation products are stayed in the cracking residual oil with liquid form, only on catalyzer, generate the solid coke of trace, and catalyzer coking speed is extremely slow, regeneration in 1～2 year once gets final product, and the reduction of catalyst activity can remedy by improving temperature of reaction; Catalyst regeneration process generally can adopt the method for burning, and bubbling air is burnt the coke on the catalyzer, makes catalyzer recover active, burns temperature and generally is controlled between 600～760 ℃.
Light ends oil of the present invention be meant boiling spread in initial boiling point～200 ℃ cracked naphtha and boiling spread at 200～350 ℃ cracked fuel oil cut, the boiling spread of heavy distillate is the cracking residual oil at 350～500 ℃ greater than 500 ℃ cuts.
The present invention compares with existing fluid catalytic cracking technology, has following advantage:
1. raw material is extensive, except that the raw material that can handle existing fluid catalytic cracking, also can handle the various vacuum residuum that existing fluid catalytic cracking can not be processed.
2. only generate the micro-solid coke that is deposited on the catalyzer, gas yield is very low, and distillate yield height, petroleum resources have obtained more reasonably using.
3. many unfavorable factors such as equipment attrition, catalyst breakage that existing fluidized-bed reactor causes be serious have been overcome.
4. catalyzer is difficult for inactivation, does not need to regenerate at any time, has saved regeneration system rapidly, makes process simplification, and investment and process cost reduce.
5. alleviate environmental pollutions such as sewage, flue gas, hot-tempered sound.
The technology contrast of the present invention and existing fluid catalytic cracking sees Table 1.
Table 1
| Technology | Fluid catalytic cracking | The present invention |
| Raw material | Heavy distillate is mixed refining and is subtracted slag | The organism that full cut vacuum residuum, various heavy distillate and various residual oil, deasphalted oil, shale oil, the dry distillation of coal obtain etc. |
| Catalyzer | Conventional catalytic cracking catalyst | Conventional catalytic cracking catalyst |
| Solvent | Do not have | Gasoline fraction, toluene etc. |
| Reactor | Fluidized-bed | Various suitable reactor types such as fixed bed, expanded bed or suspension bed |
| Temperature of reaction ℃ | ????500 | ????380～500 |
| Reaction pressure MPa | ????0.3 | ????3～15 |
| Product distributes, Wt% | ||
| Gas | ????10～20 | ????＜1.0 |
| Light ends oil | ????50～70 | ????30～60 |
| Heavy distillate | ????5～15 | ????10～20 |
| The cracking residual oil | ????20～40 | |
| Solid coke | ????6～10 | Trace (being deposited on the catalyzer) |
| The catalyst regeneration mode | Regeneration in time | Generally can adopt the method for super regeneration, (regeneration in per 1～2 year once) |
| Environment protection | Sewage. flue gas. hot-tempered sound pollution | Environmental friendliness |
Further the present invention will be described in detail below in conjunction with specific embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
With grand celebration vacuum residuum is raw material, and reaction conditions is: pressure 8MPa, and 400 ℃ of temperature, solvent is a toluene, molten slag is than 3.0, the CHZ-2 type catalyzer (micro-activity 70) that the Chang Ling catalyst plant is produced, weight space velocity 24h
-1, recycle ratio 0.2, fixed-bed reactor, reaction result sees Table 2.
Table 2
| Product yield Wt% | Cracking conversion rate Wt% | ||||
| Reacted gas | ＜200℃ | ?200～350℃ | Heavy distillate | The cracking residual oil | |
| ??0.17 | ?30.49 | ????17.25 | ????17.05 | ????35.04 | ????64.96 |
Embodiment 2
With triumph vacuum residuum is raw material, and reaction conditions is: pressure 11MPa, and 420 ℃ of temperature, solvent is a hexanaphthene, molten slag is than 2.0, the LCS-7 type catalyzer (micro-activity 76) of Lanzhou Oil Refinery production, weight space velocity 45h
-1, recycle ratio 0.3, fixed-bed reactor, reaction result sees Table 3.
Table 3
| Product yield Wt% | Cracking conversion rate Wt% | ||||
| Reacted gas | ＜200℃ | ?200～350℃ | Heavy distillate | The cracking residual oil | |
| ??0.14 | ????30.09 | ????16.54 | ????13.46 | ????39.77 | ????60.23 |
Embodiment 3
With grand celebration vacuum residuum is raw material, and reaction conditions is: pressure 14MPa, and 440 ℃ of temperature, solvent is a dimethylbenzene, molten slag is than 5.0, the CHZ-3 type catalyzer (micro-activity 74) that the Chang Ling catalyst plant is produced, weight space velocity 15h
-1, full freshening operation, fixed-bed reactor, reaction result sees Table 4.
Table 4
| Product yield Wt% | Cracking conversion rate Wt% | ||||
| Reacted gas | ＜200℃ | ?200～350℃ | Heavy distillate | The cracking residual oil | |
| ??0.90 | ????48.09 | ????30.04 | ????0.00 | ????20.97 | ????79.03 |
Embodiment 4
With triumph vacuum residuum is raw material, 420 ℃ of temperature of reaction, and reaction pressure 11MPa, solvent are diesel oil distillate, molten slag is than 3.0, catalyzer CHZ-2 (micro-activity 70), weight space velocity 30h
-1, recycle ratio 0.1, fixed-bed reactor.Experimental result sees Table 5.
Table 5
| Product yield Wt% | Cracking conversion rate Wt% | ||||
| Reacted gas | ＜200℃ | ?200～350℃ | Heavy distillate | The cracking residual oil | |
| ??0.21 | ????27.35 | ????13.67 | ????24.29 | ????34.48 | ????65.52 |
Embodiment 5
With triumph vacuum distillate (350～500 ℃) be raw material, and reaction conditions is: pressure 5MPa, and 420 ℃ of temperature, solvent is a gasoline fraction, molten slag is than 0.5, the CHZ-2 type catalyzer (micro-activity 70) of Chang Ling catalyst plant production, weight space velocity 60h
-1, not freshening operation, suspended-bed reactor, reaction result sees Table 6.
Table 6
| Product yield Wt% | Cracking conversion rate Wt% | ||||
| Reacted gas | ＜200℃ | 200～350℃ | Heavy distillate | The cracking residual oil | |
| ??1.21 | ????40.42 | ????29.22 | ????27.01 | ????2.14 | ????70.85 |
Embodiment 6
Catalyst life is investigated.With triumph vacuum residuum is raw material, 480 ℃ of temperature of reaction, and reaction pressure 4MPa, solvent are diesel oil distillate, molten slag is than 3.0, catalyzer CHZ-3 (micro-activity 74), weight space velocity 30h
-1, freshening not.When installing continuous operation after 1000 hours, catalyzer is carried out deciding the carbon analysis, the results are shown in table 7.
Table 7
| Decide the carbon condition | Catalyzer decrement (Wt%) | ||
| Parallel sample 1 | Parallel sample 2 | Parallel sample 3 | |
| ?400℃,5h | ????0.031 | ????0.032 | ????0.030 |
| ?500℃,3h | ????0.042 | ????0.043 | ????0.044 |
| ?700℃,2h | ????0.051 | ????0.049 | ????0.050 |
| ?800℃,1h | ????0.065 | ????0.063 | ????0.064 |
From deciding the carbon result as seen, coking is few on the catalyzer.Existing catalytic cracking technology regeneration rear catalyst carbon content can only reach 0.05～0.1% (Wt), and the present invention can make catalyzer after long-time the use, still can keep very high reactivity.
Claims (15)
1. catalyst cracking method, after catalytically cracked material and solvent, be forced into the emergent pressure or the supercritical pressure of described solvent, be heated to the critical temperature or the supercritical temperature of described solvent, entering reactor then contacts with catalytic cracking catalyst, carry out the catalytic cracking reaction under the supercritical state, the final reaction product enters separation system to be separated.
2. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described catalytically cracked material is the raw material that contains residual oil or heavy distillate.
3. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described catalytically cracked material is full cut vacuum residuum.
4. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described solvent is to be selected from benzene,toluene,xylene, pentamethylene, hexanaphthene, low molecule alkane, gasoline fraction, the diesel oil distillate one or more.
5. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described solvent is to be selected from toluene, dimethylbenzene, gasoline fraction, the diesel oil distillate one or more.
6. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described solvent is to be selected from gasoline fraction, the diesel oil distillate one or both.
7. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described catalyzer is that to contain with the weight percent of catalyzer be the Zeolite molecular sieve catalysis cracking catalyst of benchmark 5～15%.
8. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described reactor is fixed-bed reactor.
9. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described reaction conditions is as follows:
The molten slag ratio is 0.1～6.0; Temperature of reaction is 380～500 ℃; Reaction pressure is 3～15MPa; Weight space velocity is 15～80h
-1
10. according to the described a kind of catalyst cracking method of claim 1, it is characterized in that described reaction conditions is as follows:
The molten slag ratio is 1.0～4.0; Temperature of reaction is 400～480 ℃, and reaction pressure is 4～13MPa; Weight space velocity is 30～60h
-1
11., it is characterized in that described reaction conditions is as follows according to the described a kind of catalyst cracking method of claim 1:
The molten slag ratio is 2.0～3.0; Temperature of reaction is 420～460 ℃; Reaction pressure is 5～11MPa; Weight space velocity 40～50h
-1
12. according to the described a kind of catalyst cracking method of claim 1, the sepn process that it is characterized in that described reaction product can enter flashing tower for: reaction product after decompression, top of tower is drawn cracked gas, and the reaction product of drawing at the bottom of the flash distillation Tata enters fractionating system after decompression.In fractionating system, isolate light ends oil, heavy distillate and cracking residual oil and solvent.
13., it is characterized in that described solvent cycle use according to the described a kind of catalyst cracking method of claim 12.
14. according to the described a kind of catalyst cracking method of claim 12, it is characterized in that a described heavy distillate part goes out device, another part mixes with fresh feed as recycle stock, the cracking that circulates, and recycle ratio is 0～0.5.
15., it is characterized in that described recycle ratio is between 0.2～0.4 according to the described a kind of catalyst cracking method of claim 12.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001100548A CN1144859C (en) | 2000-01-21 | 2000-01-21 | Method for catalytic cracking residue in supercritical solvent |
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| CNB001100548A CN1144859C (en) | 2000-01-21 | 2000-01-21 | Method for catalytic cracking residue in supercritical solvent |
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| CN1144859C CN1144859C (en) | 2004-04-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774678B (en) * | 2003-02-26 | 2010-09-29 | 因特凯特设备公司 | Method and apparatus for metering catalyst in a fluid catalytic cracking catalyst injection system |
| CN102876370A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Hydrocracking method of residual oil |
| CN103282464A (en) * | 2010-12-28 | 2013-09-04 | Sk新技术株式会社 | Hydrocracking process of heavy hydrocarbon distillates using supercritical solvent |
| CN109628134A (en) * | 2019-02-15 | 2019-04-16 | 华东理工大学 | Method for regulating and controlling heavy oil molecules structure |
-
2000
- 2000-01-21 CN CNB001100548A patent/CN1144859C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774678B (en) * | 2003-02-26 | 2010-09-29 | 因特凯特设备公司 | Method and apparatus for metering catalyst in a fluid catalytic cracking catalyst injection system |
| CN103282464A (en) * | 2010-12-28 | 2013-09-04 | Sk新技术株式会社 | Hydrocracking process of heavy hydrocarbon distillates using supercritical solvent |
| CN103282464B (en) * | 2010-12-28 | 2015-01-21 | Sk新技术株式会社 | Hydrocracking process of heavy hydrocarbon distillates using supercritical solvent |
| US9550947B2 (en) | 2010-12-28 | 2017-01-24 | Sk Innovation Co., Ltd | Hydrocracking process of heavy hydrocarbon distillates using supercritical solvent |
| CN102876370A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Hydrocracking method of residual oil |
| CN109628134A (en) * | 2019-02-15 | 2019-04-16 | 华东理工大学 | Method for regulating and controlling heavy oil molecules structure |
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| CN1144859C (en) | 2004-04-07 |
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