CN1916119A - Technical flow of hydrogenation of gasolene through catalytic cracking full distillate - Google Patents
Technical flow of hydrogenation of gasolene through catalytic cracking full distillate Download PDFInfo
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Abstract
This invention discloses a method for hydrogenating fully catalytically cracked (FCC) gasoline. The method comprises: performing heat exchange between the reaction product and a mixture of FCC gasoline and liquid hydrocarbon, introducing into a TMD three-stage reactor, reacting at 320-420 deg.C under 1.5-6.0 MPa in the presence of hydrogen and F0-3558FCC hydrogenation catalyst, separating and stabilizing to obtain the gasoline product. The temperature increase of the reacting bed can be controlled by injecting either cold hydrogen or quenching oil corresponding to the highest temperature of M section in the reactor not higher than 15 deg.C or higher than 15 deg.C. The method can provide clean and environmentally friendly gasoline product, and has such advantages as simple process, stable operation, low energy consumption and no need for separating light and heavy fractions of FCC gasoline.
Description
Technical field
The invention belongs to petrochemical complex gasoline refining technical field, relate to technical flow of hydrogenation of gasolene through catalytic cracking full distillate.
Background technology
Gasoline is as the main raw material of main petroleum products and motor car engine, just be subjected at present influence from environmental protection and automotive engineering progress double factor, main western countries such as America and Europe put into effect Europe III, Europe IV new gasoline standard in succession, and 12 developed countries have taken the lead in adopting Europe IV new gasoline standard.China's white gasoline objectionable impurities control criterion comes into effect, and wherein the olefin(e) centent regulation is not more than 35% (v).From on July 1st, 2005, the gasoline products of China will adopt EUROIII Emission Standard.
Reason owing to historical development, catalytic cracking (FCC) gasoline accounts for 75% of China's gasoline, and the content of sulphur in the catalytically cracked gasoline and alkene accounts for total sulfur content and more than 90% and 80% of total olefin content in the commercial gasoline respectively, so the production problem of China's clean gasoline finally is summed up as the problem that cleans of FCC gasoline.At present (the main means that clean gasoline adopted v) are to use and fall olefin catalytic cracking catalyst and auxiliary agent less than 35% in order to produce olefin(e) centent, but brought the rising of dry gas and coke productive rate thus, liquid yield descends, a series of problems such as octane value reduction make the economy of catalytic cracking process production process decrease.What is more important, these means only can solve the olefin(e) centent problem that satisfies current clean gasoline standard code, can not solve sulfur in gasoline content problem.Abroad, because FCC gasoline accounts for the ratio less (about 1/3) of commercial gasoline, desulfurating and reducing olefinic hydrocarbon content is a research theme always, the primary study gasoline hydrogenation modifying.US4397739, CN1621495A, CN1521241A have proposed before the hydrotreatment, at first gasoline rectifying are become light constituent and heavy constituent, heavy constituent are carried out the method for specific hydrogenating desulfurization again.Also there is deficiency in above-mentioned technology, and that is exactly to reduce more for a long time at product requirement alkene, still can not avoid the too much loss of octane value, and the hydrogenation saturation of olefins also can increase the hydrogen consumption greatly, and flow process is complicated.The processing method of alkene falls in the hydrogenating desulfurization that CN1597865A, CN200410074058.7 have proposed a kind of full cut FCC inferior patrol, this method has simple, the easy handling of flow process, can make full use of reaction heat, prolong the catalyst runs cycle, liquid receives advantages such as higher relatively, that the hydrogen consumption is low, but gasoline octane rating and liquid are received and are not also reached ideal value.Above technology all is that processing method and catalyzer are described in detail, and technical process is not had or seldom description.
Summary of the invention
By the analysis and research the deficiencies in the prior art, the present invention proposes that a kind of flow process is simple, running is stable, turndown ratio is big, the full distillation gasoline hydrogenation modifying process of the FCC flow process of liquid hydrocarbon recycle to extinction.See accompanying drawing 1.
Liquid hydrocarbon with full cut inferior patrol of FCC and reaction generation, through with a series of heat exchange such as reaction product (or heating), enter three sections reactors of TMD, under hydrogen existence and certain temperature, pressure condition, with the special catalyst contact reacts, take place that diolefine, alkene are saturated, reactions such as isomerization, aromizing and desulfurization, the resultant content of olefin in gasoline is reduced, sulphur content reduces, octane value does not reduce substantially, liquid is received high, through separating, stablizing, reaches satisfactory clean gasoline at last.
Feed gasoline (1) is mixed with recycle hydrogen (3) after hydrogenation fresh feed pump (2) boosts to 1.5～6.0MPa with liquid hydrocarbon (28), then with D section reaction product through about interchanger (4) heat exchange to 168 ℃, be warming up to 160～240 ℃ through interchanger (5) and the heat exchange of M2 section reaction product again, enter T section reactor (6) and carry out pre-treatment.T section reactor volume air speed is 0.5～15h
-1, hydrogen-oil ratio is 200～800: 1.T section reaction product is after entering M1 section reaction feed process furnace (8) after interchanger (7) heat exchange and being warming up to 320～420 ℃, order enters M1 reactor (9), M2 reactor (10) carries out the hydro-upgrading reaction, reaction pressure is 1.5～6.0MPa, and reaction velocity is 0.5～8.0h
-1, hydrogen-oil ratio is 200～800: 1.M2 section reaction product elder generation and the heat exchange of T section reaction product after one stock oil interchanger (5) heat exchange of M2 section reaction product, enter D section reactor (11) and carry out the post-refining reaction again.Temperature of reaction is 160～320 ℃, and reaction pressure is 2.3～2.5MPa, and reaction velocity is 0.5～8.0h
-1Hydrogen-oil ratio is 200～800: 1, and (reaction can not drop into D section reactor during for the initial stage, last stage reaction, come into operation when falling the alkene weak effect), D section reaction product and stock oil are through about interchanger (4) heat exchange to 168 ℃, successively enter reaction product air cooler (12), reaction product aftercooler (13), after condensation is cooled to 40 ℃, enters reaction product high-pressure separator (14) and carry out gas-liquid separation.
The high-pressure separator gas phase enters circulating hydrogen compressor (16) and boosts after entering circulating hydrogen compressor inlet branch flow container (15) separatory.The compressor outlet high pressure hydrogen is divided into three the tunnel, one the tunnel enters M1, M2 section reactor middle part as cold hydrogen (17), one the tunnel as recycle hydrogen Flow-rate adjustment usefulness (18), and another Lu Yuxin hydrogen (19) mixes the back and is mixed into reactor as recycle hydrogen and feed gasoline, liquid hydrocarbon.The high-pressure separator liquid phase is as stabilizer tower (20) charging, enters stabilizer tower with oil at the bottom of the stabilizer tower through about stabilizer tower feed exchanger (21) heat exchange to 96 ℃.
Stablize cat head oil gas after stablizing cat head condensate cooler (22) and being cooled to 40 ℃, enter stable return tank of top of the tower (23) and carry out gas-liquid separation, the gas phase gas that acts as a fuel enters self-produced gas train, one the tunnel as stablizing trim the top of column, return to feed gasoline by another road (25) after stablizing cat head reflux pump (24) and boosting for liquid phase.At the bottom of oil one tunnel returned tower at the bottom of the stabilizer tower after stablizing bottom reboiler (26) heating, another Lu Xianyu high-pressure separator liquid phase was through the heat exchange of stabilizer tower feed exchanger, again after gasoline products water cooler (27) is chilled to 40 ℃, as Q-grade gasoline product carrying device.
When the temperature rise of M reactor bed is no more than under 15 ℃ of situations, can pass through the mode controlling reactor bed temperature of liquid hydrogen injection in certain scope, when the reactor bed temperature rise surpasses when requiring, can reduce the reactor outlet temperature by the mode of playing quenching oil (26), control its temperature of reaction, prevent overtemperature.Oil at the bottom of the stabilizer tower after the quenching oil employing is cold is squeezed into reactor through chilling oil pump (29).
Compared with prior art, the present invention has following advantage:
(1) liquid hydrocarbon that adopts the feed gasoline hydrogenation reaction to generate loops back the flow process that enters reactor among the feed gasoline, makes that liquid hydrocarbon reaches balance in the reaction, thereby no longer generates liquid hydrocarbon, increases yield of gasoline.
(2) adopt the FO-3558FCC gasoline hydrogenation modifying catalyst of this technical process and Fushun petrochemical corporation (complex), hydrocarbon alkene, the higher full distillation gasoline of FCC inferior of sulphur content can be processed as high-quality clean gasoline product.Can with the alkene of the full distillation gasoline of FCC by 55% (v) reduce to 35% (and v), desulfurization degree is more than 85%, the octane value of gasoline products constant substantially (or loss is less than 1.0 units), yield of gasoline is more than 99.5%.
(3) technical process is simple, and stable operation does not need FCC gasoline again by separating the weight component.
(4) Btu utilization is reasonable, utilizes the heat exchange step by step of reaction product and raw material, has made full use of reaction heat.
(5) D section reaction is the post-refining reactor, and when reaction reaches latter stage, catalyst for refining is active to descend greatlyyer, in the time of can not meeting the demands, D section reactor is dropped into, and still can obtain qualified product.
(6) means of controlling reactor bed temperature overtemperature are many, except that liquid hydrogen injection, also can play quenching oil, promptly when the reaction beginning, the catalyzer initial activity is very strong, and reaction temperature rising may be very big, causes reactor batch temperature to surpass prescribed value, at this moment can open the chilling oil pump by interlocking and inject quenching oil, with control reaction temperature to reactor.
(7) drop into and do not drop into D section reactor, heat transfer problem has all been considered in technical process, and means are more.
Description of drawings:
Fig. 1 is technical flow of hydrogenation of gasolene through catalytic cracking full distillate figure.
Embodiment:
Embodiment 1
Present embodiment has provided the reaction conditions and the reaction result of 200,000 tons of/year FCC gasoline hydrogenation of total effluent upgrading industrial experiment device designs.
Catalytic cracking full distillate quality of gasoline specification:
Research octane number (RON) 90.3
Olefin(e) centent 50～55% (v)
Flow 25000kg/h
Gasoline endpoint＜195 ℃
Catalyzer: the FO-3558FCC of Fushun petrochemical corporation (complex) gasoline hydrogenation modifying catalyst (generation+two generations) or other catalyzer of similar techniques index is arranged.
The stable gasoline specification of quality:
Research octane number (RON) 90.0
Olefin(e) centent＜35% (v)
Flow 24918kg/h
Alkene descends 20 percentage points
Liquid yield 99.67%
Because olefin(e) centent is more in the feed gasoline, so present embodiment adopts two M reactors in series flow processs.Concrete implementing procedure: feed gasoline and liquid hydrocarbon mix with recycle hydrogen after hydrogenation fresh feed pump P-101/1.2 boosts to 3.2MPa, and recycle hydrogen is 13816Nm
3/ h, then with D section reaction product through 168 ℃ of E-101 heat exchange, be warmed up to 240 ℃ through E-102/1.2 and the heat exchange of M2 section reaction product again, enter T section reactor and carry out pretreatment reaction, liquid hourly space velocity is 12h
-1, hydrogen-oil ratio is 300: 1, and T section reaction product is after E-103/1.2 and the heat exchange of M2 reaction product, and after entering M1 section reactor feed process furnace F-101 and being warming up to 420 ℃, order enters M1, M2 section reactor carries out the hydro-upgrading reaction.The M1 temperature of reaction is 420 ℃, and reaction pressure is 2.55MPa (G), and liquid hourly space velocity is 3h
-1, hydrogen-oil ratio is 300: 1; The M2 temperature of reaction is 420 ℃, and reaction pressure is 2.40MPa (G), and liquid hourly space velocity is 1h
-1, hydrogen-oil ratio is 300: 1.M2 section reaction product enters D section reactor and carries out the post-refining reaction through M2 reaction product-stock oil interchanger E-102/1.2 heat exchange to 300 ℃.D section reaction product and stock oil are through about E-101 heat exchange to 180 ℃, successively enter reaction product air cooler A101, after reaction product water cooler EW-101 condensation is cooled to 40 ℃, enter reaction product high-pressure separator V-101 and carry out gas-liquid separation, after high-pressure separator V-101 gas phase enters circulating hydrogen compressor inlet branch flow container V-102 separatory, enter circulating hydrogen compressor K-101/1.2 and boost to 3.1MPa, compressor K-101/1.2 outlet high pressure hydrogen is divided into three the tunnel, one the tunnel enters M1 as cold hydrogen, M2 section reactor middle part, one the tunnel as recycle hydrogen Flow-rate adjustment usefulness, and another Lu Yuxin hydrogen mixes the back as recycle hydrogen and feed gasoline, liquid hydrocarbon enters reactor after mixing.
High-pressure separator V-101 liquid phase is as the stabilizer tower charging, enters stabilizer tower T-101 with oil at the bottom of the stabilizer tower after 96 ℃ of stabilizer tower feed exchanger E-104 heat exchange.
Stabilizer tower T-101 cat head oil gas is cooled to 40 ℃ through stablizing cat head condensate cooler EW-103, enter and stablize return tank of top of the tower V-104 and carry out gas-liquid separation, the V-104 gas phase gas that acts as a fuel enters self-produced gas train, liquid phase is boosted behind the 1.0MPa through stablizing cat head reflux pump P-102/1.2, one the tunnel as stablizing trim the top of column, and another road is circulated in the feed gasoline.Oil one tunnel is at the bottom of returning tower after the stabilizer tower reboiler E-105 heating at the bottom of the stabilizer tower, another Lu Xianyu high-pressure separator liquid phase is through stabilizer tower feed exchanger E-104 heat exchange, after 40 ℃ of gasoline products water cooler EW-102 coolings, send at device again as the Q-grade gasoline product.
Be no more than when M reactor bed peak temperature rise under 15 ℃ the situation, can pass through the mode controlling reactor bed temperature of liquid hydrogen injection in certain scope, when if the reactor bed peak temperature rise surpasses claimed range, can reduce the reactor outlet temperature by the mode of playing quenching oil, control its temperature of reaction, prevent overtemperature.Oil at the bottom of the stabilizer tower of the cold back of quenching oil employing, P-103/1.2 squeezes into reactor through the chilling oil pump.
The operation result of matter industrial experiment device.
Catalytic cracking full distillate quality of gasoline specification:
Research octane number (RON) 88.5
Olefin(e) centent 37.7% (v)
Aromaticity content 13.3% (v)
Saturated hydrocarbon content 49.1% (v)
Sulphur content 110 μ g/g
Flow 18750kg/h
10% 52 ℃ of flow processs
30％ 65℃
50％ 85℃
90％ 155℃
Catalyzer: the FO-3558FCC of Fushun petrochemical corporation (complex) gasoline hydrogenation modifying catalyst (generation) or other catalyzer of similar techniques index is arranged.
The stable gasoline specification of quality:
Research octane number (RON) 88.8
Olefin(e) centent 30.3% (v)
Aromaticity content 15.8% (v)
Saturated hydrocarbon content 53.9% (v)
Sulphur content 20.2 μ g/g
Flow 18675kg/h
Alkene descends 7.4 percentage points
Desulfurization degree 81.64%
Yield of gasoline 99.6%
10% 51 ℃ of flow processs
30％ 72℃
50％ 96℃
90％ 166℃
Because olefin(e) centent is lower in the feed gasoline, so present embodiment adopts single M section reactor, and D instead do not come into operation, and can reach the quality product requirement.
Brief description of the process: feed gasoline and liquid hydrocarbon boost to 2.5MPa through hydrogenation fresh feed pump P-101/1.2, be warming up to about 120 ℃ through stock oil-interchanger E-101 of second-stage reaction product and the heat exchange of second-stage reaction product, mix with recycle hydrogen, mixture changes the back temperature again through stock oil-second-stage reaction product secondary heat exchange device E-102 and the heat exchange of second-stage reaction product about 170 ℃ with three-way control valve control.Change the back material and enter first stage reactor R-101 as an anti-charging.The first stage reactor reaction pressure is 2.2MPa, and reaction velocity is 12h
-1, the catalyzer model is F0-3558T.One section reaction product enters second-stage reaction process furnace F-101 and heats up after 365 ℃, enters second stage reactor R-102.The second stage reactor reaction pressure is 2.0MPa, and reaction velocity is 2.1h
-1, the catalyzer model is F0-3558M.The second-stage reaction product after successively entering reaction product air cooler EA-101/1.2, reaction product water cooler E-104 condensation and being cooled to 40 ℃, enters reaction product and divides flow container V-101 respectively through about E-101, E-102 heat exchange to 110 ℃.The V-101 gas phase,, is mixed with the feed gasoline liquid hydrocarbon after circulating hydrogen compressor K-101/1.2 boosts to 2.5MPa with after new hydrogen mixes as recycle hydrogen.Liquid phase, is compressed into into separation column T-101 through at the bottom of oil heat exchanger E-103 and the separation column at the bottom of separation column charging-separation column about oil heat exchange to 90 ℃ certainly as the separation column charging.T-101 top oil gas enters fractionation return tank of top of the tower V-103 after fractionation cat head condensate cooler E-105 is cooled to 40 ℃.The V-103 gas phase gas that acts as a fuel enters gas train, and liquid phase is returned the fractionation cat head as backflow after fractionation cat head reflux pump P-102/1.2 boosts to 1.3MPa.Oil is after oil pump P-103/1.2 at the bottom of the separation column extracts out and boosts to 1.5MPa at the bottom of the separation column, and a part is at the bottom of returning separation column after the reboiler furnace heating at the bottom of the separation column, for separation column provides thermal source; Another part is after E-103 heat exchange, gasoline products water cooler E-106 are cooled to 40 ℃, as the gasoline products carrying device.
Claims (5)
1, catalytic gasoline hydrogenation modifying process flow process, it is characterized in that: the full distillation gasoline of FCC and liquid hydrocarbon process and reactor product heat exchange, enter three sections reactors of TMD, hydrogen exist and 320～420 ℃ of temperature, 1.5～6.0MPa pressure condition under, FO-3558FCC gasoline hydrogenation modifying catalyst contact reacts with the production of Fushun petrochemical corporation (complex), and, generate Q-grade gasoline through separating, stablizing.
2, according to claim 1 described catalytic gasoline hydrogenation modifying process flow process, it is characterized in that: the catalytically cracked gasoline liquid hydrocarbon that reaction generates through hydro-upgrading is circulated among the reaction raw materials, in reactor, make liquid hydrocarbon reach balance, reaction is not carried out to the direction that generates liquid hydrocarbon, thereby increased the yield of gasoline.
3, according to claim 1 described catalytic gasoline hydrogenation modifying process flow process, it is characterized in that: at first the full distillation gasoline of FCC mixes with recycle hydrogen, then with the heat exchange of D section reaction product, enter T section reactor with the heat exchange of M section reaction product again and carry out pretreatment reaction, reaction pressure is 1.5～6.0MPa, and volume space velocity is 0.5～15.0h
-1Hydrogen-oil ratio is 200～800: 1, the catalyzer of T section reactor is the FO-3558FCC gasoline hydrogenation modifying catalyst of Fushun petrochemical corporation (complex), T section reaction product and the heat exchange of M section reaction product, entering M section reaction feed process furnace then is heated to 320～420 ℃ and enters M section reactor and carry out hydro-upgrading reaction, reaction pressure is 1.5～6.0MPa, and hydrogen-oil ratio is 200～800: 1, and volume space velocity is 0.5～4.0h
-1The catalyzer of M section reactor is the FO-3558FCC gasoline hydrogenation modifying catalyst of Fushun petrochemical corporation (complex); Directly enter D section reactor after M section reaction product and the feed gasoline heat exchange and carry out the post-refining reaction, temperature of reaction is 320～420 ℃, and reaction pressure is 1.5～6.0MPa, and hydrogen-oil ratio is 200～800: 1, and volume space velocity is 0.5～8.0h
-1, the catalyzer of D section reactor is the FO-3558FCC gasoline hydrogenation modifying catalyst of Fushun petrochemical corporation (complex); D section reaction product through with the feed gasoline heat exchange after, successively enter the reaction product high-pressure separator through air cooler, aftercooler, carry out gas-liquid separation.The gas phase that high-pressure separator is come out is through recycle compressor, mix the back with new hydrogen and use as recycle hydrogen and cold hydrogen, liquid phase through with enter stabilizer tower after the oily heat exchange at the bottom of the stabilizer tower, the high-pressure separator service temperature is 35～40 ℃; Stablize cat head oil gas after stablizing the cat head condensate cooler and being cooled to 40 ℃, enter and stablize return tank of top of the tower and carry out gas-liquid separation, the gas phase gas that acts as a fuel enters self-produced gas train, liquid phase after stablizing the cat head reflux pump and boosting one the tunnel as stablizing trim the top of column, another road is returned to feed gasoline, at the bottom of oil one tunnel returns tower at the bottom of the stabilizer tower after stablizing the bottom reboiler heating, another Lu Xianyu high-pressure separator liquid phase is through the heat exchange of stabilizer tower feed exchanger, again after the gasoline products water cooler is chilled to 40 ℃, as Q-grade gasoline product carrying device.
4, according to claim 3 described catalytic gasoline hydrogenation modifying process flow processs, it is characterized in that: M section reactor should be according to one or two reactor of how much establishing of olefin(e) centent in the feed gasoline, when olefin(e) centent in the feed gasoline 48% (when v) following, with a reactor; When olefin(e) centent in the feed gasoline 48% (when v) above, with two reactors in series.
5, according to claims 1 described catalytic gasoline hydrogenation modifying process flow process, it is characterized in that: be no more than when M section reactor bed peak temperature rise under 15 ℃ the situation, can control the reaction bed temperature rise in certain scope by the mode of liquid hydrogen injection.If when the reactor bed peak temperature rise surpasses 15 ℃, can reduce the reactor outlet temperature by the mode of playing quenching oil, oil at the bottom of the stabilizer tower after the quenching oil employing is cold is squeezed into reactor through pump.
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| CN102234540A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工集团公司 | Hydrogenation method and apparatus for center fractions of pyrolysis gasoline |
| CN102234541A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工集团公司 | Energy-saving pyrolysis gasoline full-cut hydrogenation method and device |
| CN103805235A (en) * | 2012-11-03 | 2014-05-21 | 中国石油化工股份有限公司 | Wet-process starting method of hydrogenation device, low-energy-consumption hydrogenation technology and hydrogenation equipment |
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| CN102234540A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工集团公司 | Hydrogenation method and apparatus for center fractions of pyrolysis gasoline |
| CN102234541A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工集团公司 | Energy-saving pyrolysis gasoline full-cut hydrogenation method and device |
| CN102234541B (en) * | 2010-05-07 | 2013-07-17 | 中国石油化工集团公司 | Energy-saving pyrolysis gasoline full-cut hydrogenation method and device |
| CN102234540B (en) * | 2010-05-07 | 2013-09-11 | 中国石油化工集团公司 | Hydrogenation method and apparatus for center fractions of pyrolysis gasoline |
| CN103805235A (en) * | 2012-11-03 | 2014-05-21 | 中国石油化工股份有限公司 | Wet-process starting method of hydrogenation device, low-energy-consumption hydrogenation technology and hydrogenation equipment |
| CN103805235B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Wet-process starting method of hydrogenation device, low-energy-consumption hydrogenation technology and hydrogenation equipment |
| CN106782002A (en) * | 2015-11-25 | 2017-05-31 | 中国石油天然气股份有限公司 | Gas production training system |
| CN106782002B (en) * | 2015-11-25 | 2019-10-11 | 中国石油天然气股份有限公司 | Gas production training system |
| CN114874808A (en) * | 2021-05-17 | 2022-08-09 | 德明·罗曼·尼古拉耶维奇 | Catalytic processing method and device for light hydrocarbon fraction |
| CN114874808B (en) * | 2021-05-17 | 2023-10-17 | 德明·罗曼·尼古拉耶维奇 | Light hydrocarbon fraction catalytic processing method and device thereof |
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