CN1258581C - Upgrading method and system of reducing olefinic hydrocation and increasing octane rating for catalytic gasoline - Google Patents
Upgrading method and system of reducing olefinic hydrocation and increasing octane rating for catalytic gasoline Download PDFInfo
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- CN1258581C CN1258581C CN 02123656 CN02123656A CN1258581C CN 1258581 C CN1258581 C CN 1258581C CN 02123656 CN02123656 CN 02123656 CN 02123656 A CN02123656 A CN 02123656A CN 1258581 C CN1258581 C CN 1258581C
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Abstract
The present invention relates to a modification method and a system thereof for reducing the olefin content and enhancing the octane value of catalytic gasoline. In the method, an auxiliary lifting pipe reactor with an independent sedimentation and steam stripping system is additionally arranged in a reaction-regeneration system of a heavy oil catalytic cracking device; catalytic modification reaction is carried out to full fractions or heavy fractions of catalytic cracking gasoline by establishing a secondary condensing system at the tower top of a fractionating tower; modified oil gas enters a single oil gas system for carrying out the separation of modified products for reducing the olefin content and enhancing the octane value. The technology can reduce the olefin content of catalytic cracking gasoline below 35(V)%, enhances research octane values by 3 units and satisfies environment protection requirements.
Description
Technical field:
The invention discloses a kind of catalyzed conversion method for modifying and system that reduces catalytic cracking gasoline olefine content and improve its octane value, belong to the catalytic conversion process method of petroleum hydrocarbon, relate to petrochemical industry.
Background technology:
In recent years since, the environmental regulation of countries in the world has all proposed the requirement of increasingly stringent to the quality of gasoline, diesel oil, and is especially more and more harsher to the requirement of the indexs such as olefin(e) centent, sulphur content and benzene content of gasoline.Therefore, become the main impellent that promotes that every oil Refining Technologies further advances from the requirement of environmental protection aspect, and comparatively traditional catalytic cracking technology stands in the breach especially.
Conventional catalytic cracking reaction process mainly may further comprise the steps: (1) fresh feed oil mixes with recycle stock after heat exchange, nozzle by the riser reactor bottom injects, in riser reactor, contact, vaporize immediately and react with high-temperature regenerated catalyst from revivifier.The residence time of oil gas in riser tube is very short, generally promptly enters settling vessel after several seconds, is isolated by cyclonic separator to leave reactor behind the catalyzer of carrying secretly and go follow-up fractionating system.(2) the long-pending catalyzer that coke is arranged, promptly reclaimable catalyst falls into following stripping stage by settling vessel; The multilayer chev(e)ron baffle is housed in the stripping stage and feeds superheated vapour in the bottom, in the reclaimable catalyst hole and the oil gas between the granules of catalyst displaced by water vapor and return settling vessel; Reclaimable catalyst behind stripping enters revivifier by inclined tube to be generated.(3) the main effect of revivifier is the carbon deposit that generates because of reaction on the burning-off catalyzer, and activity of such catalysts is recovered; The air of regeneration usefulness is supplied with by main air blower, and the grid distributor of air below revivifier enters the catalyzer dense-phase bed; Catalyzer after the regeneration, promptly regenerated catalyst falls into upflow tube, sends reactor cycles back to through regenerator sloped tube and uses; After regenerated flue gas is isolated the catalyzer of carrying secretly through cyclonic separator, after cigarette machine system recoveries portion of energy, enter atmosphere.
At present, China's motor spirit is still based on catalytically cracked gasoline, and data shows that China's catalytically cracked gasoline accounts for the amount of gasoline product up to 90%.The volume fraction of alkene is 45%～60% in the catalytically cracked gasoline, considerably beyond the gasoline standard of new prescription.Though this gasoline has higher octane value, its poor heat stability easily forms colloid; Also can increase the quantity of toxic substance such as active hydro carbons thing and polyenoid in the discharge after the burning.In addition, along with the continuous heaviness and the poor qualityization of catalytically cracked stock, the sulphur content in its gasoline products, nitrogen content are also increasing; Can increase SO after the burning
xAnd NO
xDischarging, environmental pollution is serious.
Hydrofining is a kind of effective measure that address the above problem, and realizes the catalytic reforming of oil product by hydrofining under hydrogen pressure, reaches desulfurization, denitrogenation, alkene is saturated and aromatic hydrocarbons is saturated purpose, to improve oil quality, to satisfy environmental requirement.But present domestic most oil refining enterprises are not to lack hydrorefined means, are exactly the not enough or shortage hydrogen source of hydrorefined processing power.So it is unpractical that the catalytically cracked gasoline that accounts for commercial gasoline 90% all improves its quality by hydrofining, and the hydrofining meeting brings the loss of gasoline octane rating.Other research report also mainly is to reduce the olefin(e) centent of catalytically cracked gasoline, as petroleum naphtha etherificate, catalytically cracked gasoline desulfurating and reducing olefinic hydrocarbon, catalytic gasoline hydrogenation isomery aromizing and catalytic gasoline hydrogenation desulfurization-reformation etc., these methods and technology or complex process, investment are greatly, many refinerys adopt still very big difficulty, that is that all right is ripe for Technology, does not realize industrialization.
Summary of the invention:
Main purpose of the present invention provides a kind of method for modifying and system of gasoline catalyzing and olefine reducing boosting of octane rating, with the olefin(e) centent of reduction catalytically cracked gasoline, and the octane value of raising gasoline;
Another object of the present invention provides a kind of method for modifying and system of gasoline catalyzing and olefine reducing boosting of octane rating, simplifies and improves the processing method that alkene falls in catalytically cracked gasoline, reduces the technology cost, is beneficial to realize industrialization.
The objective of the invention is to realize by the following method:
A kind of method for modifying of gasoline catalyzing and olefine reducing boosting of octane rating which comprises at least following steps:
Step 1: full cut of raw gasline or last running enter auxiliary upgrading riser reactor with water vapour from the bottom, contact, gasify, mix and react with high temperature regeneration agent from former catalytic cracking unit revivifier;
Step 2: oil gas, water vapour with catalyzer by auxiliary upgrading riser reactor, to the outlet of upgrading riser reactor, by efficient fast gas-solid separator with upgrading oil gas and catalyst separating;
Step 3: the upgrading oil gas after the separation enters simple and easy separation system, isolates rich gas and reformulated gasoline.
The actual conditions of described catalytic reforming reaction is as follows:
Temperature of reaction is 350～550 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
Reaction times is 2.0～10.0s;
Reaction pressure is 0.1～0.4Mpa.
The last running of described raw gasline is obtained by the B-grade condensation system.When obtaining the last running of catalytic cracking raw gasline, the raw gasline lighting end that obtains is further upgrading also.
In the modifying catalytically cracked gasoline process, enter former revivifier after entering the simple and easy settling vessel newly established and stripping stage with the catalyzer of upgrading gas-oil separation.
To the full fraction upgrading of raw gasline, the reformulated gasoline of then isolating rich gas directly enters absorbing-stabilizing system; To raw gasline last running upgrading, the reformulated gasoline of then isolating rich gas with enter absorbing-stabilizing system after the raw gasline lighting end mixes.
Described upgrading reacts the catalyzer that employed catalyzer is former heavy oil catalytic cracking unit, comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst at least.
A kind of reforming system of gasoline catalyzing and olefine reducing boosting of octane rating, which comprises at least, in the reaction-regeneration system rapidly of heavy oil catalytically cracking equipment, set up and have independent sedimentation stripping system subsidiary riser reactive system, and coupled upgrading oil and gas separating system; Wherein, the subsidiary riser reactive system is used for catalytically cracked gasoline is carried out catalytic reforming, and the upgrading oil and gas separating system is used to separate reformulated gasoline and rich gas.
Also be included in the B-grade condensation system that sets up on the conventional condensation cooling system of original fractionator overhead in the described heavy oil catalytically cracking equipment, be used to obtain raw gasline last running, also can obtain the full cut of raw gasline.
Described subsidiary riser reactive system is to constitute from a high-temperature regenerated catalyst logistics inclined tube and a riser reactor that the revivifier of original heavy oil catalytically cracking equipment is drawn; This riser reactor exit portion enters the sedimentation stripping system, and outlet is provided with efficient fast gas-solid separator.
The upgrading oil and gas separating system is: simple and easy washing knockout tower cat head connects condensate cooler, links to each other with desuperheating washing medium interchanger at the bottom of the tower.
The desuperheating washing medium is recycle stock or heavy gas oil in the described simple and easy washing knockout tower.
Technology advantage of the present invention is: because reformulated gasoline goes out device after entering independent separation system, and do not mix with the catalytically cracked gasoline of main riser tube, so return the olefin(e) centent of full cut of the raw gasline of upgrading riser tube or last running and be exactly the full cut of raw gasline that main riser tube comes out or the olefin(e) centent of last running, just gasoline olefin initial reaction concentration is higher in the upgrading riser tube, like this, needed processing condition will comparatively relax, and the component that upgrading is crossed repeatedly circulates in the upgrading riser reactor, the loss of upgrading process will reduce, and needs the amount of gasoline of upgrading also can reduce.
Description of drawings:
Fig. 1 is a basic principle schematic of the present invention;
Fig. 2 is a general flow chart of the present invention.
Embodiment:
The present invention will be further described below in conjunction with accompanying drawing and specific embodiment:
As shown in Figure 2, the operation of former catalytic-cracking reaction system is constant, be that raw material 1 enters main riser tube 2 with water vapour from the bottom, with be 460～530 ℃ by water vapour 4 steam stripped high temperature regeneration agent 5 in temperature of reaction from revivifier 3, the heavy oil feedstock preheating temperature is 160～250 ℃, catalyzer oil plant weight ratio is 5～8, catalyst activity is 50～65, reaction times is 2.5～3.0s, reaction pressure is to contact under the situation of 0.1～0.4Mpa, gasification, mix and reaction, oil gas, water vapour passes through main riser reactor 2 with catalyzer, revolve 7 separately to the outlet of main riser reactor by efficient fast gas-solid separator 6 and settling vessel top with main reaction oil gas and catalyzer, catalyzer enters stripping stage 9 through settling vessel 8, enters former revivifier 3 through behind the stripping.Main reaction oil gas 10 leaves settling vessel 8 and enters main fractionating tower and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock and slurry oil.
Raw gasline is as follows by the process description that fractionator overhead B-grade condensation system isolates last running (cut point is 60～80 ℃): raw gasline and rich gas 27 are come out by the top of separation column 28,29 condensations of process condenser are cooled to enter after 50～60 ℃ separating tank 30 and carry out the separation of Oil, Water, Gas, and condensed water 31 detaches separating tank 30 by condensate pump 32.The product liquid that condensation is got off is raw gasline last running 33, extracts out from separating tank 30 through raw gasline double distilled wheel cylinder 34, and a part refluxes 35 as the top of separation column 28, and another part 36 further is cooled to 40 ℃ through supercooler 37.If to the full fraction upgrading of raw gasline, at this moment valve 50 is opened, valve 51 is closed, and raw gasline last running 36 and raw gasline lighting end 47 are mixed into the full cut of raw gasline 49 backs (promptly 11) and enter the upgrading of newly establishing among the present invention and carry out upgrading with service hoisting pipe reactor 12; If to raw gasline last running upgrading, at this moment valve 51 is opened, valve 50 is closed, raw gasline last running 48 (promptly 11) can directly enter the upgrading that the present invention newly establishes and carry out upgrading with service hoisting pipe reactor 12, at this moment enter absorbing-stabilizing system after the reformulated gasoline 25 that petroleum naphtha 47 can be directly with the upgrading oil and gas separating system of newly establishing from the present invention comes out mixes, also can carry out earlier as behind the upgradings such as petroleum naphtha etherificate, isomery aromizing, enter absorbing-stabilizing system again with after reformulated gasoline 25 that the upgrading oil and gas separating system of newly establishing from the present invention comes out mixes.Uncooled oil gas 38 process condensers 39 condensations of coming out from separating tank 30 are cooled to enter after 40 ℃ separating tank 40 and carry out the separation of Oil, Water, Gas, and condensed water 41 detaches separating tank 40 by condensate pump 42.The uncooled oil gas that comes out from separating tank 40 is rich gas 43, enters rich gas compressor.The condensate oil of being separated by separating tank between the pneumatic press machine 44 turns back to separating tank 40.The product liquid that condensation is got off in the separating tank 40 is a petroleum naphtha 45, after being extracted out by petroleum naphtha pump 46, or mix with raw gasline last running 36 and to carry out upgrading after helping cut raw gasline 49, or entering follow-up system mixes with reformulated gasoline 25.
Referring to Fig. 1, Fig. 2, raw gasline 11 or raw gasline are by the isolated last running 11 of fractionator overhead B-grade condensation system (cut point is 60～80 ℃), enter auxiliary upgrading riser reactor 12 from the bottom with water vapour, with the high temperature regeneration agent 14 that promotes by water vapour 13 from former catalytic cracking unit revivifier 3 be 350～550 ℃ in temperature of reaction, the gasoline stocks preheating temperature is 40～200 ℃, catalyzer oil plant weight ratio is 2～20, catalyst activity is 55～65, reaction times is 2.0～10.0s, reaction pressure is to contact under the situation of 0.1～0.4Mpa, gasification, mix and reaction, oil gas, water vapour, is separated upgrading oil gas and catalyzer by efficient fast gas-solid separator 15 to the outlet of upgrading riser reactor by auxiliary upgrading riser reactor 12 with catalyzer.Catalyzer enters and newly establishes settling vessel 16 and stripping stage 17, enters former revivifier 3 through behind the stripping.Upgrading oil gas 18 leaves settling vessel 16 and enters the upgrading oil and gas separating system that is made of washing knockout tower 19, condensate cooler 20, catch pot 21, desuperheating washing medium interchanger 22 and recycle pump 23, isolates rich gas 24 and reformulated gasoline 25.If to the full fraction upgrading of catalytic cracking raw gasline, reformulated gasoline 25 can directly enter absorbing-stabilizing system; If upgrading is carried out in last running to the catalytic cracking raw gasline, reformulated gasoline 25 enters absorbing-stabilizing system after will mixing with the lighting end 47 (this part also can be carried out upgrading, as etherificate, isomery aromizing etc.) of raw gasline here again so.Desuperheating and washing catalyst powder are carried out by desuperheating washing medium interchanger 22 and 23 pairs of superheated upgradings of recycle pump oil gas in washing knockout tower 19 bottoms, and 26 for carrying the desuperheating washing medium of a small amount of upgrading heavy constituent, can be recycle stock or heavy gas oil.
The used catalyzer of the present invention can be any catalyzer that is applicable to catalytic cracking process, i.e. modifying catalytically cracked gasoline reaction is realized by former heavy oil catalytic cracking unit catalyzer.For example, amorphous silicon aluminium catalyzer or molecular sieve catalyst; Wherein, the active ingredient of molecular sieve catalyst is selected from one or more in Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 series zeolite that contains or do not contain rare earth and/or phosphorus or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1, a kind of method for modifying of gasoline catalyzing and olefine reducing boosting of octane rating is characterized in that: which comprises at least following steps:
Step 1: full cut of raw gasline or last running enter auxiliary upgrading riser reactor with water vapour from the bottom, contact, gasify, mix and react with the high temperature regeneration agent from former catalytic cracking unit revivifier, described auxiliary upgrading riser reactor is to be made of a high-temperature regenerated catalyst logistics inclined tube of drawing from the revivifier of original heavy oil catalytically cracking equipment and a riser reactor; This riser reactor exit portion enters the sedimentation stripping system, and outlet is provided with efficient fast gas-solid separator; The actual conditions of described reaction is as follows:
Temperature of reaction is 350～550 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
Reaction times is 2.0～10.0s;
Reaction pressure is 0.1～0.4Mpa;
Step 2: oil gas, water vapour with catalyzer by auxiliary upgrading riser reactor, to the outlet of upgrading riser reactor, by efficient fast gas-solid separator with upgrading oil gas and catalyst separating;
Step 3: the upgrading oil gas after the separation enters simple and easy separation system, isolates rich gas and reformulated gasoline, and described simple and easy separation system is: simple and easy washing knockout tower cat head connects condensate cooler, links to each other with desuperheating washing medium interchanger at the bottom of the tower.
2, the method for modifying of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 1 is characterized in that: the last running of described raw gasline is obtained by the B-grade condensation system.When obtaining the last running of catalytic cracking raw gasline, the also further upgrading of the raw gasline lighting end that obtains.
3, the method for modifying of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 1, it is characterized in that: in the modifying catalytically cracked gasoline process, enter former revivifier after entering the simple and easy settling vessel newly established and stripping stage with the catalyzer of upgrading gas-oil separation.
4, the method for modifying of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 1 is characterized in that: to the full fraction upgrading of raw gasline, the reformulated gasoline of then isolating rich gas directly enters absorbing-stabilizing system; To raw gasline last running upgrading, the reformulated gasoline of then isolating rich gas with enter absorbing-stabilizing system after the raw gasline lighting end mixes.
5, the method for modifying of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 1, it is characterized in that: described upgrading reacts the catalyzer that employed catalyzer is former heavy oil catalytic cracking unit, comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst at least.
6, a kind of reforming system of gasoline catalyzing and olefine reducing boosting of octane rating, it is characterized in that: which comprises at least, in the reaction one regeneration system of heavy oil catalytically cracking equipment, set up and have independent sedimentation stripping system subsidiary riser reactive system, and coupled upgrading oil and gas separating system; Wherein, the subsidiary riser reactive system is to be made of a high-temperature regenerated catalyst logistics inclined tube of drawing from the revivifier of original heavy oil catalytically cracking equipment and a riser reactor; This riser reactor exit portion enters the sedimentation stripping system, and outlet is provided with efficient fast gas-solid separator, and this subsidiary riser reactive system is used for catalytically cracked gasoline is carried out catalytic reforming; Described upgrading oil and gas separating system is: simple and easy washing knockout tower cat head connects condensate cooler, links to each other with desuperheating washing medium interchanger at the bottom of the tower, and this upgrading oil and gas separating system is used to separate reformulated gasoline and rich gas.
7, the reforming system of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 6 is characterized in that: the actual conditions of described catalytic reforming reaction is as follows:
Temperature of reaction is 350～550 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
Reaction times is 2.0～10.0s;
Reaction pressure is 0.1～0.4Mpa.
8, the reforming system of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 6, it is characterized in that: also be included in the B-grade condensation system that sets up on the conventional condensation cooling system of original fractionator overhead in the described heavy oil catalytically cracking equipment, be used to obtain raw gasline last running or obtain the full cut of raw gasline.
9, the reforming system of a kind of gasoline catalyzing and olefine reducing boosting of octane rating according to claim 6 is characterized in that: the desuperheating washing medium is recycle stock or heavy gas oil in the described simple and easy washing knockout tower.
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| CN 02123656 CN1258581C (en) | 2002-07-05 | 2002-07-05 | Upgrading method and system of reducing olefinic hydrocation and increasing octane rating for catalytic gasoline |
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| CN 02123656 CN1258581C (en) | 2002-07-05 | 2002-07-05 | Upgrading method and system of reducing olefinic hydrocation and increasing octane rating for catalytic gasoline |
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| CN1465663A CN1465663A (en) | 2004-01-07 |
| CN1258581C true CN1258581C (en) | 2006-06-07 |
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