CN1258580C - Upgrading method and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline - Google Patents
Upgrading method and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline Download PDFInfo
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- CN1258580C CN1258580C CN 02123655 CN02123655A CN1258580C CN 1258580 C CN1258580 C CN 1258580C CN 02123655 CN02123655 CN 02123655 CN 02123655 A CN02123655 A CN 02123655A CN 1258580 C CN1258580 C CN 1258580C
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Abstract
The present invention relates to a modification method and a device thereof for deeply reducing olefin and increasing the octane value of catalytic cracking gasoline. In the method, a catalytic modification reactor is additionally arranged in a reaction-regeneration system of a heavy oil catalytic cracking device; the catalytic modification reaction is carried out to cracked gasoline fractions; modified oil gas enters a single oil gas fractionating system for carrying out the separation of modification products for deeply reducing olefin contents and increasing octane values; the modified catalytic cracking gasoline fractions can be crude gasoline full fractions, crude gasoline light fractions or crude gasoline heavy fractions; the fractions are obtained by establishing a secondary condensing system on the tower top of a fractionating tower; the new catalyzing modification reactor is composed of a lower part lifting pipe and an upper part bubbling fluidized bed and is provided with an independent steam stripping system and an independent sedimentation system. The modification technology can reduce the olefin content of catalytic cracking gasoline below 20(V)%, enhances research octane values by 5 units and satisfies high environmental rule requirements.
Description
Technical field:
The invention discloses a kind of method for modifying and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline, belong to the catalytic conversion process of petroleum hydrocarbon, relate to petrochemical industry.
Background technology:
In recent years since, increasingly stringent along with environmental requirement, the U.S., Japan and European various countries have issued new gasoline standard in succession, the volumn concentration that in December, 1999, Chinese State Bureau of Environmental Protection was also formulated alkene in " motor spirit objectionable impurities standard " regulation gasoline is not more than 35, research octane number (RON) is not less than 90, the volumn concentration of aromatic hydrocarbons is not more than 40, and sulphur content is less than 800ppm; And stipulate to rise in Beijing on July 1st, 2000, big cities such as Shanghai, Guangzhou implement, rose on January 1st, 2003 in China and implement, expectation is after 2005 particularly when the " green Games " in 2008, to carry out stricter standard: (v) below the %, octane value is higher 25 for olefin(e) centent.
The octane value of alkene is higher, but chemical property is active, NO in volatilization back and the atmosphere
xMix,, atmosphere is caused severe contamination through the poisonous photo-chemical smog of solar ultraviolet irradiation formation based on ozone; In addition, when olefin(e) centent is high in the gasoline, can cause that electronic fuel injection engine nozzle, feed valve carbon deposit are serious, cause controlled deviation, cause fuel oil consumption to increase, therefore, the control olefin content in gasoline is a compliance with environmental protection requirements.But, the main source of China's motor spirit is a catalytic cracking process at present, ratio that data shows catalytically cracked gasoline in the Chinese commodity gasoline is arranged up to 90%, and olefin(e) centent is 45～55 (v) % is far above the gasoline standard of new prescription in the catalytically cracked gasoline.So, reduce olefin(e) centent, produce the urgent task that the clean gasoline product becomes current petroleum refining industry.
In order to reduce the olefin(e) centent of catalytically cracked gasoline; petroleum refining industry generally takes following measure: the pre-hydrotreatment of fcc raw material, employing olefine lowering catalyst and optimization catalytic cracking unit operational condition etc.; but effect is limited; content of olefin in gasoline maximum 10～12 the volume percentage points that can only descend; can't reach the requirement of new gasoline standard; on the other hand, octane value can reduce about 2 units usually, and transformation efficiency also has to a certain degree decline and catalytic diesel oil degradation simultaneously.It is the another kind of method of producing the low olefin-content clean gasoline that catalytically cracked gasoline is carried out independent upgrading: as petroleum naphtha etherificate, catalytically cracked gasoline desulfurating and reducing olefinic hydrocarbon, catalytic gasoline hydrogenation isomery aromizing and catalytic gasoline hydrogenation desulfurization～reformation etc., but these methods and technology or complex process, investment are greatly, are difficult to be applicable to China petroleum refining industry; Perhaps Technology is immature, is difficult to realize industrialization in a short time.
Summary of the invention:
Main purpose of the present invention provides a kind of method for modifying and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline, 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline, 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline which comprises at least following steps:
Step 1: the full cut of catalytic cracking raw gasline, lighting end or last running and water vapour enter the catalytic reforming reactor of setting up together from the bottom, contact, gasify, mix with high temperature regeneration agent from former catalytic cracking unit revivifier and carry out the upgrading reaction;
Step 2: upgrading oil gas with leave settling vessel after reclaimable catalyst separates in settling vessel;
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 350～500 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
The reaction times that promotes pipeline section is 1.0～10.0s;
The fluidized-bed weight space velocity is 1～1000h
-1
Reaction pressure is 0.1～0.4Mpa.
The lighting end of described raw gasline and last running are obtained by the B-grade condensation system, and when obtaining the last running of catalytic cracking raw gasline, the raw gasline lighting end that obtains is further upgrading also.
In the described upgrading process, reclaimable catalyst enters former revivifier after entering the simple and easy settling vessel newly established, stripping stage, or enters the stripping stage of former catalytic cracking unit.
To the full fraction upgrading of raw gasline, then directly enter absorbing-stabilizing system with the isolating reformulated gasoline of rich gas; To raw gasline last running upgrading, then with the isolating reformulated gasoline of rich gas with enter absorbing-stabilizing system after the lighting end of raw gasline mixes; Upgrading is carried out in the raw gasline lighting end, then with the isolating reformulated gasoline of rich gas with enter absorbing-stabilizing system again after the last running of raw gasline 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline which comprises at least, and sets up the catalytic reforming reactor in the reaction-regeneration system of heavy oil catalytically cracking equipment, and the coupled simple and easy separation system of upgrading oil gas; 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 of the fractionator overhead foundation of original conventional condensation cooling system in the described heavy oil catalytically cracking equipment, be used to obtain raw gasline last running and lighting end, also can obtain the full cut of raw gasline.
Described catalytic reforming reactor adds the top bubbling fluidized bed by the bottom riser tube and constitutes, by set up an inclined tube of drawing the high-temperature regenerated catalyst logistics to link to each other with the revivifier of original heavy oil catalytically cracking equipment from the revivifier of original heavy oil catalytically cracking equipment from the riser tube bottom, this catalytic reforming reactor top bubbling fluidized bed is partly with independently sedimenting system and stripping system, is provided with secondary cyclone in this sedimenting system of setting up.
The upgrading oil and gas separating system consists of: 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 that is adapted to simple and easy washing knockout tower is recycle stock or heavy gas oil.
The advantage of Technology of the present invention goes out device after entering independent separation system owing to reformulated gasoline, and do not mix with the catalytically cracked gasoline of main riser tube, so return the olefin(e) centent of the full cut of the raw gasline of upgrading riser tube or last running or lighting end and be exactly the full cut of raw gasline that main riser tube comes out or the olefin(e) centent of last running or lighting end, 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 mode 1 of the present invention;
Fig. 3 is a general flow chart mode 2 of the present invention;
Fig. 4 is a general flow chart mode 3 of the present invention.
Embodiment:
Describe the present invention below in conjunction with accompanying drawing in detail by specific embodiment:
Referring to Fig. 1, Fig. 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 behind stripping.Main reaction oil gas 10 leaves settling vessel 8 and enters the separation that main fractionating tower carries out rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil.
Catalytically cracked gasoline cut 11, be full cut of raw gasline or raw gasline last running (＞60～80 ℃) or raw gasline lighting end (＜80～110 ℃), enter new catalytic reforming reactor 12 from the bottom with water vapour, with the high temperature regeneration agent 14 that promotes by water vapour 13 from revivifier 3 be 350～500 ℃ 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, promoting the pipeline section reaction times is 1.0～10.0s, and the fluidized-bed reactor weight space velocity is 1～1000h
-1Reaction pressure is to contact, gasify, mix and react under the situation of 0.1～0.4Mpa, oil gas, water vapour pass through new catalytic reforming reactor 12 with catalyzer, upgrading oil gas separates in newly establishing settling vessel 15 with catalyzer, catalyzer enters stripping stage 16, enters former revivifier 3 through reclaimable catalyst 17 behind the stripping.Upgrading oil gas 18 leaves settling vessel 15 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 to catalytic cracking raw gasline last running upgrading, reformulated gasoline 25 enters absorbing-stabilizing system after will mixing with raw gasline lighting end 47 (this cut also can carry out upgrading, as etherificate, isomery aromizing etc.) here so; If to catalytic cracking raw gasline lighting end upgrading, so reformulated gasoline 25 here will with enter absorbing-stabilizing system again after raw gasline last running 48 mixes.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 to carry the desuperheating washing medium of a small amount of upgrading heavy constituent, can be recycle stock or heavy gas oil.
Raw gasline is as follows by the process description that fractionator overhead B-grade condensation system isolates lighting end (＜80～110 ℃), last running (＞60～80 ℃): oil gas 27 (comprising raw gasline and rich gas) is come out by the top of separation column 28,29 condensations of process condenser are cooled to suitable temp, and (if to raw gasline last running upgrading, this temperature is 50～60 ℃; If to raw gasline lighting end upgrading, this temperature is 62～80 ℃) after enter separating tank 30 and carry out the separation of Oil, Water, Gas, 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 35 refluxes 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, and valve 51 is closed, and raw gasline last running 36 and raw gasline lighting end 47 are mixed into and enter new catalytic reforming reactor 12 behind the full cut 49 of raw gasline (being gasoline fraction charging 11) and carry out upgrading; If to raw gasline last running upgrading, at this moment valve 51 is opened, valve 50 is closed, raw gasline last running 48 (being gasoline fraction charging 11) can directly enter new catalytic reforming reactor 12 and carry out upgrading, at this moment raw gasline lighting end 47 can directly with after the reformulated gasoline 25 that comes out from newly-increased upgrading oil and gas separating system mixes enter absorbing-stabilizing system, after also can carrying out upgrading earlier as aspects such as petroleum naphtha etherificate, isomery aromizing, again with enter absorbing-stabilizing system after mixing from reformulated gasoline 25; If upgrading is carried out in the raw gasline lighting end, at this moment valve 51 is opened, valve 50 is closed, and raw gasline lighting end 47 or 49 (being gasoline fraction charging 11) can directly enter new catalytic reforming reactor 12 and carry out upgrading, last running at this moment 48 can with enter absorbing-stabilizing system after reformulated gasoline 25 mixes.
The mode that the present invention gets back to former catalytic cracking unit for the reclaimable catalyst that is come out by the new catalytic reforming reactor of setting up also comprises following 2 kinds: the reclaimable catalyst of being drawn by the stripping stage of newly establishing among Fig. 1 can be incorporated in the stripping stage of former catalytic cracking unit, can obtain the mode of Fig. 3 thus; The stripping stage of newly establishing among Fig. 1 can not established, and reclaimable catalyst can directly be incorporated in the stripping stage of former catalytic cracking unit by reactor fluidisation bed bed, can obtain the mode of Fig. 4 thus.
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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline is characterized in that: which comprises at least following steps:
Step 1: the full cut of catalytic cracking raw gasline, lighting end or last running and water vapour enter the catalytic reforming reactor of setting up together from the bottom, contact, gasify, mix with high temperature regeneration agent from former catalytic cracking unit revivifier and carry out the upgrading reaction; Described catalytic reforming reactor adds the top bubbling fluidized bed by the bottom riser tube and constitutes, by set up an inclined tube of drawing the high-temperature regenerated catalyst logistics to link to each other with the revivifier of original heavy oil catalytically cracking equipment from the revivifier of original heavy oil catalytically cracking equipment from the riser tube bottom, this catalytic reforming reactor top bubbling fluidized bed is partly with independently sedimenting system and stripping system, is provided with secondary cyclone in this sedimenting system of setting up; The actual conditions of described upgrading reaction is as follows:
Temperature of reaction is 350～500 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
The reaction times that promotes pipeline section is 1.0～10.0s;
The fluidized-bed weight space velocity is 1～1000h
-1
Reaction pressure is 0.1～0.4Mpa;
Step 2: upgrading oil gas with leave settling vessel after reclaimable catalyst separates in settling vessel;
Step 3: the upgrading oil gas after the separation enters simple and easy separation system, isolates rich gas and reformulated gasoline; Described separation system consists of: 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 1, it is characterized in that: the lighting end of described raw gasline and last running are 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 1, it is characterized in that: in the described upgrading process, reclaimable catalyst enters former revivifier after entering the simple and easy settling vessel newly established, stripping stage, or enters the stripping stage of former catalytic cracking unit.
4, the method for modifying of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 1 is characterized in that: to the full fraction upgrading of raw gasline, then directly enter absorbing-stabilizing system with the isolating reformulated gasoline of rich gas; To raw gasline last running upgrading, then with the isolating reformulated gasoline of rich gas with enter absorbing-stabilizing system after the lighting end of raw gasline mixes; Upgrading is carried out in the raw gasline lighting end, then with the isolating reformulated gasoline of rich gas with enter absorbing-stabilizing system again after the last running of raw gasline mixes.
5, the method for modifying of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline 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 heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline, it is characterized in that: which comprises at least, in the reaction one regeneration system of heavy oil catalytically cracking equipment, set up the catalytic reforming reactor, and the coupled simple and easy separation system of upgrading oil gas; Described catalytic reforming reactor adds the top bubbling fluidized bed by the bottom riser tube and constitutes, by set up an inclined tube of drawing the high-temperature regenerated catalyst logistics to link to each other with the revivifier of original heavy oil catalytically cracking equipment from the revivifier of original heavy oil catalytically cracking equipment from the riser tube bottom, this catalytic reforming reactor top bubbling fluidized bed is partly with independently sedimenting system and stripping system, is provided with secondary cyclone in this sedimenting system of setting up; Described upgrading oil and gas separating system consists of: 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; 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.
7, the reforming system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 6 is characterized in that: the actual conditions of described catalytic reforming reaction is as follows:
Temperature of reaction is 350～500 ℃;
The gasoline stocks preheating temperature is 40～200 ℃;
Catalyzer oil plant weight ratio is 2～20;
Catalyst activity is 55～65;
The reaction times that promotes pipeline section is 1.0～10.0s;
The fluidized-bed weight space velocity is 1～1000h
-1
Reaction pressure is 0.1～0.4Mpa.
8, the reforming system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 6, it is characterized in that: the B-grade condensation system that also is included in the fractionator overhead foundation of original conventional condensation cooling system in the described heavy oil catalytically cracking equipment, be used to obtain raw gasline last running and lighting end, perhaps obtain the full cut of raw gasline.
9, the reforming system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline according to claim 6 is characterized in that: the desuperheating washing medium that is adapted to simple and easy washing knockout tower is recycle stock or heavy gas oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123655 CN1258580C (en) | 2002-07-05 | 2002-07-05 | Upgrading method and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline |
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| CN 02123655 CN1258580C (en) | 2002-07-05 | 2002-07-05 | Upgrading method and system of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline |
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| CN1465662A CN1465662A (en) | 2004-01-07 |
| CN1258580C true CN1258580C (en) | 2006-06-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425674C (en) * | 2003-10-31 | 2008-10-15 | 中国石油化工股份有限公司 | Catalytic converting method for improving petrol octane number |
| CN101164684B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101164685B (en) * | 2006-10-20 | 2010-10-06 | 中国石油化工股份有限公司 | Combined quickly fluidized bed reactor |
| CN103805256B (en) * | 2012-11-07 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil reactive distillation process |
| CN104611049B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil reactive distillation process |
| CN106800947A (en) * | 2017-02-28 | 2017-06-06 | 中石化炼化工程（集团）股份有限公司 | A kind of method for modifying of catalytically cracked gasoline |
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