CN101245257A - Sidetrack etherification method integrated with catalytic cracking absorption stable system - Google Patents
Sidetrack etherification method integrated with catalytic cracking absorption stable system Download PDFInfo
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- CN101245257A CN101245257A CNA2007100639212A CN200710063921A CN101245257A CN 101245257 A CN101245257 A CN 101245257A CN A2007100639212 A CNA2007100639212 A CN A2007100639212A CN 200710063921 A CN200710063921 A CN 200710063921A CN 101245257 A CN101245257 A CN 101245257A
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Abstract
The invention provides a lateral line etherification method which integrates a catalytic cracking absorbing stabilizing system; hydrocarbon etherification raw materials are sent into a catalytic cracking stabilizer for fractionation, the catalytic cracking stabilizer is provided with a lateral line discharge hole from the position about 95 percent of the height to about 50 percent of the height of the stabilizer, the liquid material and fatty alcohol from the lateral line discharge hole are mixed together to be sent into an etherification reactor for reaction with the effect of etherification catalyst, the reaction products are sent into the stabilizer for fractionation without separating from the lateral line feeding hole under the lateral line discharge hole, separated liquefied gas can be obtained from the top of the stabilizer, while stabilized gasoline containing ether compound is obtained from the bottom of the stabilizer. The method fully makes use of the mass transfer and heat transfer conditions of the catalytic cracking stabilizing system, which does not only reduce the energy and material consumption, but also obtains the stabilized gasoline with low content of olefin, the high octane value and qualified vapor pressure.
Description
Technical field
The present invention relates to the method for a kind of hydrocarbon raw material and Fatty Alcohol(C12-C14 and C12-C18) generation etherification reaction, more particularly, is a kind of hydro carbons etherification method and the combined method of absorption-stabilization system by catalytic cracking.
Background technology
Along with the increasingly stringent of legislations of environmental protection, countries in the world and area are also strict day by day for the restriction of olefin(e) centent in the gasoline in recent years, and market for the needs of high-grade gasoline also along with the development of automobile market constantly increases.China implements the national standard (GB 17930-1999) of " unleaded gasoline for vehicle " in China since in January, 2003, and this criteria limit olefin(e) centent is not more than 35 volume %, estimates that this restriction also can further reduce from now on.Nearly 80% gasoline of China is from catalytic cracking process, and all the other gasoline components are less, the mediation ability; China's catalytically cracked gasoline presents the feature of high olefin, low arene content, and about 40～50 volume %, aromaticity content does not have oxygenatedchemicals less than 20 volume % to olefin(e) centent basically usually.And olefin component and Fatty Alcohol(C12-C14 and C12-C18) are reacted the corresponding ether of generation, and be to reduce olefin content in gasoline and vapour pressure, improve gasoline octane rating, improve the effective ways of quality of gasoline.
Iso-butylene etherificate technology, the C of at present existing comparative maturity
5Cut etherificate technology and petroleum naphtha etherificate technology, the industrial overwhelming majority are to be catalyst for etherification with the storng-acid cation exchange resin, and it is that heteropolyacid with loading type is a catalyst for etherification that a spot of industrial application is also arranged.Typical etherification technology generally includes several sections such as purification of raw materials, etherification reaction and Methanol Recovery.Diolefine and alkali nitrogen are the poisonous substances of catalyst for etherification, therefore for the raw material of etherification that cuts out strict demand are arranged from full distillation gasoline.Existing C
5Cut etherificate technology and petroleum naphtha etherificate technology all are to cut out respective components as raw material of etherification earlier from full distillation gasoline, and raw material of etherification is generally again by caustic wash desulfuration, and washing dealkalize nitrogen after the pre-treatment such as removing alkadiene by selective hydrogenation, carries out etherification reaction again.Because the processing step of prior art is more, need repeat cooling, step-down, heats and boost, so the operation energy consumption height.
US 5015782 discloses a kind of processing method of producing ether compound, and this method is with C
4And C
4Above isomeric olefine is that raw material of etherification adopts the two-stage method technical process, at first section is two placed in-line fixed-bed reactor, with the tart mesoporous molecular sieve as catalyzer, second section is catalytic distillation tower, with the storng-acid cation exchange resin is catalyst for etherification, and the raw material of etherification after the washing carries out the part etherification reaction at first section, removes alkali nitrogen, diolefine and metal impurities simultaneously, carry out further etherificate at second section subsequently, obtain methyl tertiary butyl ether (MTBE) at last.This method is an independently etherification technology process, does not combine with catalytic cracking process.
US 5188725 discloses the method for a kind of fluid catalytic cracking process and etherification reaction combination, this method is a rapid processing method of successive multistep, mainly comprise heavier hydrocarbon feeds the regeneration of first fluidized bed catalytic cracking, catalytic cracking catalyst, olefin feed the second fluidized-bed etherificate, to the second fluidized-bed fresh makeup catalyst and the catalyzer of extracting the second fluidized-bed part inactivation out to steps such as first class bed bioreactors.Mainly adopt macro-porous zeolite catalyst at the first fluidized bed, second fluidized-bed mainly adopts central hole zeolite catalyst.In addition, olefin feed will be through the pre-treatment step of washing before carrying out etherification reaction.This method flow complexity, processing step is many.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of and the integrated side line etherification method of absorption-stabilization system by catalytic cracking.
Method provided by the invention is that the hydro carbons raw material of etherification enters the catalytic cracking stabilizer tower and carries out fractionation, described catalytic cracking stabilizer tower 50% is provided with the side line discharge port from tower height 95% to tower height, from liquid phase stream that the side line discharge port is extracted out with enter methyltertiarvbutyl ether reactor after Fatty Alcohol(C12-C14 and C12-C18) mixes, under the effect of catalyst for etherification, react, its resultant of reaction enters tower without separation again by the side entry feed mouth that is positioned at side line discharge port below and carries out fractionation, separating obtained liquefied gas is obtained by the cat head of stabilizer tower, obtain containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower, described catalyst for etherification is selected from storng-acid cation exchange resin, in molecular sieve catalyst and the heteropolyacid catalyst one or more.
The present invention has carried out etherification reaction process and existing absorption-stabilization system by catalytic cracking to combine effectively, make full use of the temperature that absorption-stabilization system by catalytic cracking has, pressure, mass transfer and heat transfer condition and carried out etherification reaction, not only be huge energy consumption and the running cost of enterprise's saving, and obtained olefin(e) centent reduction, octane value raising and the qualified stable gasoline of vapour pressure.The present invention has adaptability preferably for higher these characteristics of domestic catalytic cracking gasoline olefine content, can be refinery's production high-grade gasoline more flexibility of operation is provided.
Description of drawings
Fig. 1 is the schematic flow sheet of the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
Fig. 2 is the schematic flow sheet of the integrated side line etherification method that pre-etherificate is arranged of provided by the invention and absorption-stabilization system by catalytic cracking.
Fig. 3 is a methyltertiarvbutyl ether reactor arranged in series mode synoptic diagram in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
Fig. 4 is the methyltertiarvbutyl ether reactor mode I synoptic diagram that is arranged in parallel in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
Fig. 5 is the methyltertiarvbutyl ether reactor mode II synoptic diagram that is arranged in parallel in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
Embodiment
The integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking is: the hydro carbons raw material of etherification enters the catalytic cracking stabilizer tower and carries out fractionation, described catalytic cracking stabilizer tower 50% is provided with the side line discharge port from tower height 95% to tower height, from liquid phase stream that the side line discharge port is extracted out with enter methyltertiarvbutyl ether reactor after Fatty Alcohol(C12-C14 and C12-C18) mixes, under the effect of catalyst for etherification, react, its resultant of reaction enters tower without separation again by the side entry feed mouth that is positioned at side line discharge port below and carries out fractionation, separating obtained liquefied gas is obtained by the cat head of stabilizer tower, obtain containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower, described catalyst for etherification is selected from storng-acid cation exchange resin, in molecular sieve catalyst and the heteropolyacid catalyst one or more.
In the method provided by the invention, described hydro carbons raw material of etherification can directly enter the catalytic cracking stabilizer tower, also can carry out pre-etherificate earlier, and then enters the catalytic cracking stabilizer tower and carry out fractionation.Specifically, the hydro carbons raw material of etherification is before entering the catalytic cracking stabilizer tower, earlier being mixed into pre-methyltertiarvbutyl ether reactor with optional Fatty Alcohol(C12-C14 and C12-C18) contacts with catalyst for etherification in advance and reacts, its resultant of reaction directly enters the catalytic cracking stabilizer tower without separation and carries out fractionation, and described pre-catalyst for etherification is selected from one or more in storng-acid cation exchange resin, molecular sieve catalyst and the heteropolyacid catalyst.
Described pre-methyltertiarvbutyl ether reactor is selected from one or more the combination in fixed-bed reactor, fluidized-bed reactor and the bubbling bed reactor.The quantity of reactor is set to 1～3, can connect and/or parallel connection.The reaction conditions of described pre-etherification reaction: alcohol/hydrocarbon mass ratio (Fatty Alcohol(C12-C14 and C12-C18)/hydro carbons raw material of etherification mass ratio) is 0～0.6, temperature of reaction is 40～160 ℃, reaction pressure is 1.0～1.7MPa, and in the hydro carbons raw material of etherification, weight space velocity is 1.0～20.0h during feeding liquid
-1Pre-etherification reaction can be under the lower situation of alcohol/hydrocarbon, does not perhaps exist fully under the situation of Fatty Alcohol(C12-C14 and C12-C18) to carry out, and wherein the add-on of Fatty Alcohol(C12-C14 and C12-C18) can and suppress the situation that olefin polymer generates by the etherificate degree of depth in the pre-etherification procedure and decide.The hydro carbons raw material of etherification can remove most of diolefine and alkali nitrogen and carry out a spot of etherification reaction in pre-methyltertiarvbutyl ether reactor, can play the effect of the follow-up catalyst for etherification of protection, prolongs its work-ing life, can improve the degree of depth of etherification reaction again.
Catalytic cracking of the present invention comprises all technologies of catalytic cracking family, as fluid catalytic cracking (FCC), residual oil catalytic cracking (RFCC), catalytic pyrolysis (DCC), catalytic pyrolysis (CPP), voluminous gas and gasoline catalyzing cracking (MGG), voluminous isomeric olefine catalytic cracking (MIO), voluminous isoparaffin catalytic cracking (MIP), voluminous gas and diesel oil catalytic cracking (MGD) etc.Basic all catalytic cracking process all are made up of reaction-regeneration system, fractionating system and absorbing-stabilizing system three parts.In the catalytic cracking process device of various types, fractionating system all is the same with absorbing-stabilizing system, absorbing-stabilizing system generally includes absorption tower, desorption tower and stabilizer tower, and main effect is to utilize the method for absorption and rectifying that rich gas and raw gasline are separated into dry gas (≤C
2), liquefied gas (C
3, C
4) and stable gasoline.Conventional stabilizer tower is exactly a rectifying tower, carries out fractionation from the deethanizing gasoline of desorption tower at stabilizer tower, and overhead product is a liquefied gas, and bottom product is the qualified stable gasoline of vapour pressure.Catalytic cracking stabilizer tower of the present invention comprises the stabilizer tower of all process units of above-mentioned catalytic cracking family.
At least contain a kind of tertiary carbon alkene in the described hydro carbons raw material of etherification.Described tertiary carbon alkene is meant the monoolefine of double bond position on tertiary carbon atom, as C
4A kind of tertiary carbon alkene is only arranged, i.e. iso-butylene, C
5Two kinds of tertiary carbon alkene are arranged, i.e. 2-methyl-2-butene and 2-methyl-1-butene alkene, and C
68 kinds of tertiary carbon alkene are arranged, C
722 kinds of tertiary carbon alkene are then arranged.Etherification reaction can take place and generate low-steam pressure and high-octane ether compound in tertiary carbon alkene and Fatty Alcohol(C12-C14 and C12-C18) under the effect of catalyzer, reaction formula is as follows:
In the formula: R
1Be C
nH
2n, R
2And R
3Be alkyl.For example, the reaction of iso-butylene and methyl alcohol generates methyl tertiary butyl ether (MTBE); 2-methyl-2 butylene or 2-methyl-1-butene alkene and methyl alcohol reaction generate tert amyl methyl ether(TAME) (TAME); C
6Tertiary carbon alkene and methyl alcohol reaction can generate 4 kinds of ether compounds; C
7Tertiary carbon alkene and methyl alcohol reaction can generate 11 kinds of ether compounds.Because C
8Above tertiary carbon alkene content in gasoline is low, and reactive behavior is low, can ignore in etherification procedure of the present invention.
Described hydro carbons raw material of etherification is selected from liquefied gas, C
5In cut, catalytically cracked gasoline and the pyrolysis gasoline one or more.Described liquefied gas is meant from refinery gas and obtains C
3, C
4Component, the preferably mixture that contains four carbon atom that goes out from catalytic cracking by product and/or cracking separation of by-products, perhaps iso-butylene; C
5Cut is meant the isolated mixture that contains five carbon atoms from catalytic cracking by product and/or cracking by product; Described catalytically cracked gasoline is meant one or more the mixture in full distillation gasoline, deethanizing gasoline, stable gasoline and the petroleum naphtha (≤105 ℃) of catalytic cracking family technology; Described pyrolysis gasoline is meant the gasoline fraction from the preparing ethylene by steam cracking device.In catalytically cracked gasoline and pyrolysis gasoline, contain a large amount of C
4～C
7Multiple tertiary carbon alkene is good raw material of etherification.
Described catalytic cracking stabilizer tower 50% is provided with the side line discharge port from tower height 95% to tower height, and pairing side entry feed mouth is positioned at the below of this side line discharge port.This is because in the hydrocarbon mixture, C
4～C
7Tertiary carbon alkene boiling point is low, in tower height 50% above enrichment, so the position of side line discharge port is arranged on tower height 95% to tower height 50% place.In addition, etherification reaction is moderate thermopositive reaction, the temperature out of methyltertiarvbutyl ether reactor is higher than its temperature in, it is the temperature that stabilizer tower side entry feed temperature will be higher than the discharging of stabilizer tower side line, because feeding temperature is close with the opening for feed temperature to be the highest feeding manner of fractionation efficiency, so according to the temperature gradient distribution of stabilizer tower, pairing stabilizer tower side entry feed mouth position should be positioned at the below of this side line discharge port.
Described catalytic cracking stabilizer tower is provided with 1～4 side line discharge port, on different side line positions, in the liquid phase stream composition of tertiary carbon alkene with distribute differently, the different fractions feature of the liquid phase stream that can extract out according to side line is selectively carried out etherification reaction in methyltertiarvbutyl ether reactor; On the other hand, modulation stable gasoline and liquefied gas C flexibly
4Proportionlity between the component.Because along with tower height change from the bottom to top, C
4Concentration raises gradually, thereby can suitably select side line discharge port position, changes the ratio between liquefied gas and the stable gasoline.For example, produce liquefied gas if desired, then side line discharge port position produces stable gasoline, then inclined to one side tops, side line discharge port position if desired.
Described methyltertiarvbutyl ether reactor is selected from one or more the combination in fixed-bed reactor, fluidized-bed reactor, magnetically stabilized bed reactor, catalytic distillation tower and the bubbling bed reactor.The quantity of described methyltertiarvbutyl ether reactor is 1～4, can connect and/or parallel connection.Methyltertiarvbutyl ether reactor pattern of the present invention and arrangement mode thereof are more flexible, and multiple reactor pattern and multiple array mode are arranged, and can adapt to different situations and demand.
The reaction conditions of described etherification reaction: alcohol/hydrocarbon mass ratio (Fatty Alcohol(C12-C14 and C12-C18)/hydro carbons raw material of etherification mass ratio) is 0.1～0.6, temperature of reaction is 40～160 ℃, reaction pressure is 1.0～1.7MPa, in hydro carbons raw material of etherification (in the liquid phase stream of side line outlet), weight space velocity is 1.0～20.0h during feeding liquid
-1Temperature in the side line methyltertiarvbutyl ether reactor, promptly side line discharge port temperature is determined by the distribution of stabilizer tower natural temperature gradient.Pressure in the side line methyltertiarvbutyl ether reactor, promptly side line discharge port pressure is determined by the distribution of stabilizer tower natural pressure gradient.
Described catalytic cracking stabilizer tower: tower top temperature is 40～60 ℃, and column bottom temperature is 140～170 ℃, and pressure is 0.9～1.7MPa, and the trim the top of column ratio is 1～6.Described tower can be packing tower, sieve-tray tower, valve tray column, grid tray tower or its combination of various types.
Described Fatty Alcohol(C12-C14 and C12-C18) is selected from one or more in methyl alcohol, ethanol and the propyl alcohol.In the present invention, the optional Fatty Alcohol(C12-C14 and C12-C18) of a part enters in the pre-methyltertiarvbutyl ether reactor, another part Fatty Alcohol(C12-C14 and C12-C18) with enter in the methyltertiarvbutyl ether reactor after the side line discharging mixes.Fatty Alcohol(C12-C14 and C12-C18) adding mode and add-on are determined by the amount of needed ether compound in the product, and Fatty Alcohol(C12-C14 and C12-C18) does not contain Fatty Alcohol(C12-C14 and C12-C18) finally by completely consumed in final product.
Pre-catalyst for etherification of the present invention and catalyst for etherification are to be selected from storng-acid cation exchange resin, molecular sieve catalyst and the heteropolyacid catalyst one or more.The preferred macroporous type storng-acid cation exchange resin of described storng-acid cation exchange resin, it is through the vinylbenzene of the macroporous netlike structure of sulfonation processing and the multipolymer of divinylbenzene.Described heteropolyacid catalyst is meant heteropolyacid and corresponding loaded catalyst thereof.
Described molecular sieve catalyst comprises molecular sieve, inorganic oxide and optional clay, and each components contents is respectively: zeolite 10～50 heavy %, inorganic oxide 5～90 heavy %, clay 0～70 heavy %.The molecular sieve catalyst that is adopted among the present invention can be the catalytic cracking catalyst of the various trades mark of industry use, or has the similar catalyzer of catalytic cracking effect.When with molecular sieve catalyst during as catalyst for etherification, the catalytic cracking catalyst that preferred autocatalysis cracking reaction system is adopted.
Described molecular screening one or more in FAU type molecular sieve, MFI type molecular sieve and BEA type molecular sieve.FAU type molecular sieve comprises Y type, X type and A type, and commonly used is polytype Y zeolite; The molecular sieve of MFI structure comprises ZSM-5, titanium silicon type molecular sieve etc., and commonly used is type ZSM 5 molecular sieve; The BEA type is the Beta molecular sieve of sial type.
Described molecular sieve is to be selected from H type molecular sieve, Na type molecular sieve and the ion-exchange molecular sieve one or more.Described ion-exchange molecular sieve is meant to be selected from the molecular sieve that arbitrary metal ion carried out ion-exchange in rare earth, IB family and the group VIII.With the Y zeolite is example, can be one or more the mixture in Y zeolite, NaY type molecular sieve, rare earth Y type molecular sieve (REY), rare earth hydrogen Y zeolite (REHY), super-stable Y molecular sieves (USY) and the rare earth superstable Y-type molecular sieve (REUSY).
Described inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Go the catalytic cracking reaction regeneration system rapidly to regenerate behind the described molecular sieve catalyst inactivation.During as pre-catalyst for etherification or catalyst for etherification, the reason of its inactivation mainly is carbon deposit and the absorption of alkali nitrogen on catalyzer, therefore the molecular sieve catalyst behind the inactivation can be sent into the FCC reaction-regeneration system and regenerate with molecular sieve catalyst.So both can solve the inactivation problem of pre-catalyst for etherification and catalyst for etherification, make full use of existing catalytic cracking reaction regeneration system rapidly again, further reduce energy consumption and material consumption.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Fig. 1 is the schematic flow sheet of the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
The integrated side line etherification method technical process of provided by the invention and absorption-stabilization system by catalytic cracking is described below: enter catalytic cracking stabilizer tower 6 from the hydro carbons raw material of etherification of pipeline 1 and carry out fractionation, the liquid phase stream that the side line discharge port 22 of catalytic cracking stabilizer tower 6 is extracted out through pipeline 17 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 18 mixes, enter methyltertiarvbutyl ether reactor 20 and catalyst for etherification contact reacts through pipeline 19, to between the tower height 50%, the resultant of reaction of methyltertiarvbutyl ether reactor 20 enters catalytic cracking stabilizer tower 6 through pipeline 21 by the side entry feed mouth 23 that is positioned at side line discharge port 22 belows and carries out fractionation without separating side line discharge port 22 again at the tower height 95% of catalytic cracking stabilizer tower 6.The C that catalytic cracking stabilizer tower 6 is separating obtained
4Component is extracted out from the cat head of catalytic cracking stabilizer tower 6 by pipeline 7, and after condenser 8 condensations, a part is returned cat head through pipeline 10 as trim the top of column, another part through pipeline 9 as the liquefied gas withdrawing device.The C that catalytic cracking stabilizer tower 6 is separating obtained
5The mixture of above component and ether compound is extracted out through pipeline 11 at the bottom of by tower, after reboiler 12 heating, at the bottom of a part of tower mixture at the bottom of pipeline 14 returns tower, another part then successively through pipeline 13, condenser 15, pipeline 16 as the stable gasoline withdrawing device.
Fig. 2 is the schematic flow sheet of the integrated side line etherification method that pre-etherificate is arranged of provided by the invention and absorption-stabilization system by catalytic cracking.
The integrated side line etherification method technical process that pre-etherificate is arranged of provided by the invention and absorption-stabilization system by catalytic cracking is described below: the hydro carbons raw material of etherification from pipeline 1 can enter pre-methyltertiarvbutyl ether reactor 4 through pipeline 3 separately, perhaps mix after pipeline 3 enters pre-methyltertiarvbutyl ether reactor 4 with Fatty Alcohol(C12-C14 and C12-C18) from pipeline 2, react under pre-catalyst for etherification effect, its resultant of reaction enters catalytic cracking stabilizer tower 6 without separation through pipeline 5 and carries out fractionation.The liquid phase stream that the side line discharge port 22 of catalytic cracking stabilizer tower 6 is extracted out through pipeline 17 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 18 mixes, enter methyltertiarvbutyl ether reactor 20 and catalyst for etherification contact reacts through pipeline 19, to between the tower height 50%, the resultant of reaction of methyltertiarvbutyl ether reactor 20 enters catalytic cracking stabilizer tower 6 through pipeline 21 by the side entry feed mouth 23 that is positioned at side line discharge port 22 belows and carries out fractionation without separating side line discharge port 22 again at the tower height 95% of catalytic cracking stabilizer tower 6.The C that catalytic cracking stabilizer tower 6 is separating obtained
4Component is extracted out from the cat head of catalytic cracking stabilizer tower 6 by pipeline 7, and after condenser 8 condensations, a part is returned cat head through pipeline 10 as trim the top of column, another part through pipeline 9 as the liquefied gas withdrawing device.The C that catalytic cracking stabilizer tower 6 is separating obtained
5The mixture of above component and ether compound is extracted out through pipeline 11 at the bottom of by tower, after reboiler 12 heating, at the bottom of a part of tower mixture at the bottom of pipeline 14 returns tower, another part then successively through pipeline 13, condenser 15, pipeline 16 as the stable gasoline withdrawing device.
Fig. 3～Fig. 5 is mainly in order to the different arrangement modes of explanation side line reactor, so omitted the system of boiling again at the bottom of trim the top of column system and the tower among the figure.
Fig. 3 is a methyltertiarvbutyl ether reactor arranged in series mode synoptic diagram in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
The technical process of methyltertiarvbutyl ether reactor arranged in series mode is described below in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking: enter catalytic cracking stabilizer tower 2 from the hydro carbons raw material of etherification of pipeline 1 and carry out fractionation, tower height 95% at catalytic cracking stabilizer tower 2 locates to be provided with side line discharge port 15 between the tower height 50%, from liquid phase stream that side line discharge port 15 is extracted out through pipeline 3 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 4 mixes, enter first methyltertiarvbutyl ether reactor 6 and catalyst for etherification contact reacts through pipeline 5, its resultant of reaction is successively through pipeline 7, pipeline 9 enters second methyltertiarvbutyl ether reactor 10, the optional Fatty Alcohol(C12-C14 and C12-C18) that replenishes is successively through pipeline 8, pipeline 9 enters second methyltertiarvbutyl ether reactor 10 and carries out further etherification reaction, and its resultant of reaction enters catalytic cracking stabilizer tower 2 through pipeline 11 by the side entry feed mouth 16 that is positioned at side line discharge port 15 belows without separation again and carries out fractionation.The C that catalytic cracking stabilizer tower 2 is separating obtained
4Component is extracted separating obtained C by pipeline 12 out from the cat head of catalytic cracking stabilizer tower 2
5The mixture of above component and ether compound is extracted out through pipeline 13 at the bottom of by tower.
Fig. 4 is the methyltertiarvbutyl ether reactor mode I synoptic diagram that is arranged in parallel in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
The be arranged in parallel technical process of mode I of methyltertiarvbutyl ether reactor is described below in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking: enter catalytic cracking stabilizer tower 2 from the hydro carbons raw material of etherification of pipeline 1 and carry out fractionation, at the tower height 95% of catalytic cracking stabilizer tower 2 to locating to be provided with side line discharge port 15 and side line discharge port 17 between the tower height 50%, wherein side line discharge port 17 is positioned at the below of side line discharge port 15 and its pairing side entry feed mouth 16, from liquid phase stream that side line discharge port 15 is extracted out through pipeline 3 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 4 mixes, enter first methyltertiarvbutyl ether reactor 6 and catalyst for etherification contact reacts through pipeline 5, its resultant of reaction enters catalytic cracking stabilizer tower 2 through pipeline 7 by the side entry feed mouth 16 that is positioned at side line discharge port 15 belows without separation and carries out fractionation.From liquid phase stream that side line discharge port 17 is extracted out through pipeline 8 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 9 mixes, enter second methyltertiarvbutyl ether reactor 10 and catalyst for etherification contact reacts through pipeline 14, its resultant of reaction enters catalytic cracking stabilizer tower 2 through pipeline 11 by the side entry feed mouth 18 that is positioned at side line discharge port 17 belows without separation and carries out fractionation.The C that catalytic cracking stabilizer tower 2 is separating obtained
4Component is extracted separating obtained C by pipeline 12 out from the cat head of catalytic cracking stabilizer tower 2
5The mixture of above component and ether compound is extracted out through pipeline 13 at the bottom of by tower.
Fig. 5 is the methyltertiarvbutyl ether reactor mode II synoptic diagram that is arranged in parallel in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking.
The be arranged in parallel technical process of mode II of methyltertiarvbutyl ether reactor is described below in the integrated side line etherification method of provided by the invention and absorption-stabilization system by catalytic cracking: enter catalytic cracking stabilizer tower 2 from the hydro carbons raw material of etherification of pipeline 1 and carry out fractionation, at the tower height 95% of catalytic cracking stabilizer tower 2 to locating to be provided with side line discharge port 15 and side line discharge port 17 between the tower height 50%, wherein side line discharge port 17 is between side line discharge port 15 and its pairing side entry feed mouth 16, from liquid phase stream that side line discharge port 15 is extracted out through pipeline 3 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 4 mixes, enter first methyltertiarvbutyl ether reactor 6 and catalyst for etherification contact reacts through pipeline 5, its resultant of reaction enters catalytic cracking stabilizer tower 2 through pipeline 7 by the side entry feed mouth 16 that is positioned at side line discharge port 15 belows without separation and carries out fractionation.From liquid phase stream that side line discharge port 17 is extracted out through pipeline 8 with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 9 mixes, enter second methyltertiarvbutyl ether reactor 10 and catalyst for etherification contact reacts through pipeline 14, its resultant of reaction enters catalytic cracking stabilizer tower 2 through pipeline 11 by the side entry feed mouth 18 that is positioned at side line discharge port 17 belows without separation and carries out fractionation.The C that catalytic cracking stabilizer tower 2 is separating obtained
4Component is extracted separating obtained C by pipeline 12 out from the cat head of catalytic cracking stabilizer tower 2
5The mixture of above component and ether compound is extracted out through pipeline 13 at the bottom of by tower.
Advantage of the present invention:
(1) adopts method provided by the invention, can be enterprise and save a large amount of energy consumption and running cost.The present invention has carried out etherification reaction process and existing absorption-stabilization system by catalytic cracking to combine effectively, make full use of the temperature that absorption-stabilization system by catalytic cracking has, pressure, mass transfer and heat transfer condition and carried out etherification reaction, raw material cutting step of the prior art and feed pretreatment step had both been saved, the ether compound of producing simultaneously directly enters gasoline pool, has reduced the running cost that follow-up harmonic process needs.In addition,, also can utilize the catalytic cracking reaction regeneration system rapidly to carry out the regeneration of molecular sieve catalyst, can further cut down the consumption of energy and material consumption if adopt molecular sieve catalyst as catalyst for etherification.
(2) adopt method provided by the invention can obtain olefin(e) centent reduction, octane value raising and the qualified stable gasoline of vapour pressure.The present invention has adaptability preferably for higher these characteristics of domestic catalytic cracking gasoline olefine content, can be refinery's production high-grade gasoline more flexibility of operation is provided.
The present invention is further illustrated below by embodiment, but content not thereby limiting the invention.
Pre-methyltertiarvbutyl ether reactor and methyltertiarvbutyl ether reactor used among the embodiment are fixed-bed reactor, and used catalytic cracking stabilizer tower is a small-sized simulation stabilizer tower device, height 2.0m, filling Raschig ring filler.
The used catalyst A of embodiment is a molecular sieve catalyst, and its composition: USY is 50 weight %, and silicon sol is 15 weight %, and kaolin is 35 weight %.The used industrial trade mark of embodiment is that DOCP catalytic cracking catalyst, the industrial trade mark are that CGP-1 catalytic cracking catalyst, the industrial trade mark are that the GOR-II catalytic cracking catalyst is by the Chang Ling catalyst plant production of catalyzer branch office of China Petrochemical Industry.Storng-acid cation exchange resin Amberlyst35 is that rom Haas factory produces.The used Fatty Alcohol(C12-C14 and C12-C18) of embodiment is a methyl alcohol, is analytical pure.
The hydro carbons raw material of etherification that present embodiment adopts is the C that contains 20% iso-butylene
4Cut, C
4Enter stabilizer tower after cut and the methanol mixed, tower height 80% place at stabilizer tower is provided with the side line discharge port, after liquid phase stream that the side line discharge port is extracted out and methanol mixed, enter methyltertiarvbutyl ether reactor, A contacts with catalyst for etherification, at alcohol/hydrocarbon mass ratio 0.5,80 ℃ of temperature of reaction, reaction pressure 1.7MPa, in the liquid phase stream of side line outlet, weight space velocity is 2.0h during feeding liquid
-1Condition under react, its resultant of reaction enters and carries out fractionation in the tower without separating side entry feed mouth by tower height 50% place of stabilizer tower, cat head by stabilizer tower obtains gaseous fraction, obtain MTBE at the bottom of the tower of stabilizer tower, the operational condition of stabilizer tower is: tower top temperature is 40 ℃, and column bottom temperature is 160 ℃, pressure tower is 1.5MPa, the trim the top of column ratio is 6, and reaction result is a methanol conversion 100%, generates MTBE selectivity＞99%.
Comparative Examples 1
The explanation of this Comparative Examples is at the operational circumstances of conventional catalytic cracking stabilizer tower, and raw materials used is catalytic cracking deethanizing gasoline stocks 1.Catalytic cracking deethanizing gasoline carries out fractionation in stabilizer tower, obtain liquefied gas by cat head, by obtaining stable gasoline at the bottom of the tower, operational condition is that tower top temperature is 50 ℃, column bottom temperature is 140 ℃, and pressure tower is 1.5MPa, and the trim the top of column ratio is 5, olefin(e) centent is 48 volume % in the stable gasoline of gained, and octane value is 88.
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline 1 identical with Comparative Examples 1, enter stabilizer tower after catalytic cracking deethanizing gasoline 1 and the methanol mixed, tower height 80% place at stabilizer tower is provided with the side line discharge port, after liquid phase stream that the side line discharge port is extracted out and methanol mixed, enter methyltertiarvbutyl ether reactor, GOR-II contacts with catalytic cracking catalyst, at alcohol/hydrocarbon mass ratio 0.2,100 ℃ of temperature of reaction, reaction pressure 1.5MPa, in the liquid phase stream of side line outlet, weight space velocity is 4.0h during feeding liquid
-1Condition under react, its resultant of reaction enters and carries out fractionation in the tower without separating side entry feed mouth by tower height 50% place of stabilizer tower, the operational condition of stabilizer tower is: tower top temperature is 40 ℃, column bottom temperature is 170 ℃, pressure tower is 1.7MPa, the trim the top of column ratio is 6, obtains liquefied gas by the cat head of stabilizer tower, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.
Reaction result is that olefin(e) centent is 32 volume % in the stable gasoline of gained, and octane value is 90, compares with Comparative Examples 1, and olefin(e) centent has reduced by 16%, and octane value has improved 2 units.
Comparative Examples 2
The explanation of this Comparative Examples is at the operational circumstances of conventional catalytic cracking stabilizer tower, and raw materials used is catalytic cracking deethanizing gasoline stocks 2.Catalytic cracking deethanizing gasoline carries out fractionation in stabilizer tower, obtain liquefied gas by cat head, by obtaining stable gasoline at the bottom of the tower, operational condition is that tower top temperature is 40 ℃, column bottom temperature is 170 ℃, and pressure tower is 1.7MPa, and the trim the top of column ratio is 5, olefin(e) centent is 50 volume % in the stable gasoline of gained, and octane value is 88.
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline 2 identical with Comparative Examples 2, enter pre-methyltertiarvbutyl ether reactor after catalytic cracking deethanizing gasoline 2 and the methanol mixed, DOCP contacts with catalytic cracking catalyst, at alcohol/hydrocarbon mass ratio 0.1,120 ℃ of temperature of reaction, reaction pressure 1.5MPa, in the hydro carbons raw material of etherification, weight space velocity is 18.0h during feeding liquid
-1Condition under react.Reaction result is in alkene, olefinic polymerization selectivity≤0.5%, diolefine in the resultant of reaction≤100 μ g/g, alkali nitrogen content≤1 μ g/g.
The resultant of reaction of pre-methyltertiarvbutyl ether reactor enters stabilizer tower and carries out fractionation, tower height 60% place at stabilizer tower is provided with the side line discharge port, after liquid phase stream that the side line discharge port is extracted out and methanol mixed, enter methyltertiarvbutyl ether reactor, Amberlyst35 contacts with storng-acid cation exchange resin, at alcohol/hydrocarbon mass ratio 0.3,80 ℃ of temperature of reaction, reaction pressure 1.7MPa, in the liquid phase stream of side line outlet, weight space velocity is 4.0h during feeding liquid
-1Condition under react, its resultant of reaction enters and carries out fractionation in the tower without separating side entry feed mouth by tower height 40% place of stabilizer tower, the operational condition of stabilizer tower is: tower top temperature is 40 ℃, column bottom temperature is 170 ℃, pressure tower is 1.7MPa, the trim the top of column ratio is 5, obtains liquefied gas by the cat head of stabilizer tower, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.
Reaction result is that olefin(e) centent is 20 volume % in the stable gasoline of gained, and octane value is 93, compares with Comparative Examples 2, and olefin(e) centent has reduced by 30%, and octane value has improved 5 units.
Comparative Examples 3
The explanation of this Comparative Examples is at the operational circumstances of conventional catalytic cracking stabilizer tower, and raw materials used is catalytic cracking deethanizing gasoline stocks 3.Catalytic cracking deethanizing gasoline carries out fractionation in stabilizer tower, obtain liquefied gas by cat head, by obtaining stable gasoline at the bottom of the tower, operational condition is that tower top temperature is 40 ℃, column bottom temperature is 170 ℃, and pressure tower is 1.7MPa, and the trim the top of column ratio is 6, olefin(e) centent is 47 volume % in the stable gasoline of gained, and octane value is 88.
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline 3 identical with Comparative Examples 3, catalytic cracking deethanizing gasoline 3 enters pre-methyltertiarvbutyl ether reactor, CGP-1 contacts with catalytic cracking catalyst, 100 ℃ of temperature of reaction, reaction pressure 1.7MPa, in the hydro carbons raw material of etherification, weight space velocity is 18.0h during feeding liquid
-1Condition under react.Reaction result is in alkene, olefinic polymerization selectivity≤0.5%, diolefine in the resultant of reaction≤100 μ g/g, alkali nitrogen content≤1 μ g/g.
The resultant of reaction of pre-methyltertiarvbutyl ether reactor enters stabilizer tower and carries out fractionation, tower height 50% place at stabilizer tower is provided with the side line discharge port, after liquid phase stream that the side line discharge port is extracted out and methanol mixed, enter methyltertiarvbutyl ether reactor, Amberlyst35 contacts with storng-acid cation exchange resin, at alcohol/hydrocarbon mass ratio 0.3,60 ℃ of temperature of reaction, reaction pressure 1.7MPa, in the liquid phase stream of side line outlet, weight space velocity is 6.0h during feeding liquid
-1Condition under react, its resultant of reaction enters and carries out fractionation in the tower without separating side entry feed mouth by tower height 30% place of stabilizer tower, the operational condition of stabilizer tower is: tower top temperature is 40 ℃, column bottom temperature is 170 ℃, pressure tower is 1.7MPa, the trim the top of column ratio is 5, obtains liquefied gas by the cat head of stabilizer tower, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.
Reaction result is that olefin(e) centent is 19 volume % in the stable gasoline of gained, and octane value is 93, compares with Comparative Examples 3, and olefin(e) centent has reduced by 27%, and octane value has improved 5 units.
Claims (18)
- One kind with the integrated side line etherification method of absorption-stabilization system by catalytic cracking, it is characterized in that the hydro carbons raw material of etherification enters the catalytic cracking stabilizer tower and carries out fractionation, described catalytic cracking stabilizer tower 50% is provided with the side line discharge port from tower height 95% to tower height, from liquid phase stream that the side line discharge port is extracted out with enter methyltertiarvbutyl ether reactor after Fatty Alcohol(C12-C14 and C12-C18) mixes, under the effect of catalyst for etherification, react, its resultant of reaction enters tower without separation again by the side entry feed mouth that is positioned at side line discharge port below and carries out fractionation, separating obtained liquefied gas is obtained by the cat head of stabilizer tower, obtain containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower, described catalyst for etherification is selected from storng-acid cation exchange resin, in molecular sieve catalyst and the heteropolyacid catalyst one or more.
- 2. in accordance with the method for claim 1, it is characterized in that the hydro carbons raw material of etherification is before entering the catalytic cracking stabilizer tower, earlier being mixed into pre-methyltertiarvbutyl ether reactor with optional Fatty Alcohol(C12-C14 and C12-C18) contacts with catalyst for etherification in advance and reacts, its resultant of reaction directly enters the catalytic cracking stabilizer tower without separation and carries out fractionation, and described pre-catalyst for etherification is selected from one or more in storng-acid cation exchange resin, molecular sieve catalyst and the heteropolyacid catalyst.
- 3. in accordance with the method for claim 2, it is characterized in that described pre-methyltertiarvbutyl ether reactor is selected from one or more the combination in fixed-bed reactor, fluidized-bed reactor and the bubbling bed reactor.
- 4. in accordance with the method for claim 2, the reaction conditions that it is characterized in that described pre-etherification reaction: alcohol/hydrocarbon mass ratio is 0～0.6, and temperature of reaction is 40～160 ℃, and reaction pressure is 1.0～1.7MPa, in the hydro carbons raw material of etherification, weight space velocity is 1.0～20.0h during feeding liquid -1
- 5. according to claim 1 or 2 described methods, it is characterized in that containing at least in the described hydro carbons raw material of etherification a kind of tertiary carbon alkene.
- 6. in accordance with the method for claim 5, it is characterized in that described hydro carbons raw material of etherification is selected from liquefied gas, C 5In cut, catalytically cracked gasoline and the pyrolysis gasoline one or more.
- 7. according to claim 1 or 2 described methods, it is characterized in that described catalytic cracking stabilizer tower is provided with 1～4 side line discharge port.
- 8. according to claim 1 or 2 described methods, it is characterized in that described methyltertiarvbutyl ether reactor is selected from one or more the combination in fixed-bed reactor, fluidized-bed reactor, magnetically stabilized bed reactor, catalytic distillation tower and the bubbling bed reactor.
- 9. according to claim 1 or 2 described methods, the quantity that it is characterized in that described methyltertiarvbutyl ether reactor is 1～4, arranges with series connection and/or parallel way.
- 10. according to claim 1 or 2 described methods, the reaction conditions that it is characterized in that described etherification reaction: alcohol/hydrocarbon mass ratio is 0.1～0.6, and temperature of reaction is 40～160 ℃, and reaction pressure is 1.0～1.7MPa, in the hydro carbons raw material of etherification, weight space velocity is 1.0～20.0h during feeding liquid -1
- 11. according to claim 1 or 2 described methods, it is characterized in that described catalytic cracking stabilizer tower: tower top temperature is 40～60 ℃, column bottom temperature is 140～170 ℃, and pressure is 0.9～1.7MPa, and the trim the top of column ratio is 1～6.
- 12., it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is selected from one or more in methyl alcohol, ethanol and the propyl alcohol according to claim 1 or 2 described methods.
- 13. according to claim 1 or 2 described methods, described molecular sieve catalyst comprises molecular sieve, inorganic oxide and optional clay, each components contents is respectively: zeolite 10～50 heavy %, inorganic oxide 5～90 heavy %, clay 0～70 heavy %.
- 14. in accordance with the method for claim 13, it is characterized in that described molecular screening one or more in FAU type molecular sieve, MFI type molecular sieve and BEA type molecular sieve.
- 15. in accordance with the method for claim 14, it is characterized in that described molecular sieve is to be selected from H type molecular sieve, Na type molecular sieve and the ion-exchange molecular sieve one or more.
- 16. in accordance with the method for claim 15, it is characterized in that described ion-exchange molecular sieve is meant to be selected from the molecular sieve that arbitrary metal ion carried out ion-exchange in rare earth, IB family and the group VIII.
- 17. in accordance with the method for claim 13, described inorganic oxide is selected from silicon-dioxide and/or aluminium sesquioxide.
- 18. in accordance with the method for claim 13, it is characterized in that going the catalytic cracking reaction regeneration system rapidly to regenerate behind the described molecular sieve catalyst inactivation.
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