CN101245259B - Etherification method combined with catalytic cracking absorption stable system - Google Patents
Etherification method combined with catalytic cracking absorption stable system Download PDFInfo
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- CN101245259B CN101245259B CN2007100639208A CN200710063920A CN101245259B CN 101245259 B CN101245259 B CN 101245259B CN 2007100639208 A CN2007100639208 A CN 2007100639208A CN 200710063920 A CN200710063920 A CN 200710063920A CN 101245259 B CN101245259 B CN 101245259B
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Abstract
The invention provides a hydrocarbon etherification method which is combined with a catalytic cracking absorbing stabilizing system; after being mixed with the chosen fatty alcohol, the hydrocarbon etherification raw materials are sent into a pre-etherification reactor, and reacts with a pre-etherification catalyst in a contact way; without separation, the reaction products are directly put into catalytic cracking stabilizer after being mixed with the chosen fatty alcohol; during the reaction period in the catalytic cracking stabilizer, the reaction products react in contact with the etherification catalyst for fractionation, 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, high octane value and qualified vapor pressure; the method has great suitability towards the characteristic that domestic catalytic gasoline has high content of olefin, which can provide more operating flexibility for refineries to produce gasoline of high index.
Description
Technical field
The present invention relates to a kind ofly under the katalysis of catalyst for etherification, the method for etherification reaction takes place in hydrocarbon raw material and Fatty Alcohol(C12-C14 and C12-C18) in the catalytic cracking stabilizer tower.
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 (GB17930-1999) 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.
US5015782 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.
US5188725 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 hydro carbons etherification method a kind of and the absorption-stabilization system by catalytic cracking combination.
Method provided by the invention is the hydro carbons raw material of etherification and enter pre-methyltertiarvbutyl ether reactor after optional Fatty Alcohol(C12-C14 and C12-C18) mixes, contact with pre-catalyst for etherification and to react, its resultant of reaction is without separating and entering the catalytic cracking stabilizer tower after Fatty Alcohol(C12-C14 and C12-C18) mixes, in the conversion zone and the catalyst for etherification contact reacts of catalytic cracking stabilizer tower and carry 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 pre-catalyst for etherification and catalyst for etherification are 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
Accompanying drawing is provided by the invention and the schematic flow sheet of the hydro carbons etherification method of absorption-stabilization system by catalytic cracking combination.
Embodiment
The hydro carbons etherification method of provided by the invention and absorption-stabilization system by catalytic cracking combination is: the hydro carbons raw material of etherification with enter pre-methyltertiarvbutyl ether reactor after the Fatty Alcohol(C12-C14 and C12-C18) of choosing wantonly mixes, contact with pre-catalyst for etherification and to react, its resultant of reaction is without separating and entering the catalytic cracking stabilizer tower after Fatty Alcohol(C12-C14 and C12-C18) mixes, in the conversion zone and the catalyst for etherification contact reacts of catalytic cracking stabilizer tower and carry 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 pre-catalyst for etherification and catalyst for etherification are for being selected from storng-acid cation exchange resin, in molecular sieve catalyst and the heteropolyacid catalyst one or more.
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 pre-methyltertiarvbutyl ether reactor is fixed-bed reactor and/or fluidized-bed reactor, the preferred streams fluidized bed reactor.The quantity of reactor is set to 1～3, can connect and/or parallel connection.The reaction conditions of 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, and temperature of reaction is 40～160 ℃, and 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.
Be provided with conversion zone and rectifying section and/or stripping section in the catalytic cracking stabilizer tower of the present invention, rectifying section is positioned at the top of conversion zone, and stripping section is positioned at the below of conversion zone.Described tower can be packing tower, sieve-tray tower, valve tray column, grid tray tower or its combination of various types.Be filled with catalyst for etherification in conversion zone, tertiary carbon alkene in the raw material of etherification and Fatty Alcohol(C12-C14 and C12-C18) are when carrying out etherification reaction, and its reactant also separates with resultant, has finally obtained C by cat head
3, C
4Deng light constituent, C
5Above heavy constituent comprise that ether compound is then by extracting out at the bottom of the tower.
The conversion zone of described catalytic cracking stabilizer tower is provided with 2～6 Fatty Alcohol(C12-C14 and C12-C18) opening for feeds.In the present invention, a part of Fatty Alcohol(C12-C14 and C12-C18) is to enter stabilizer tower after the reaction effluent mixing of pre-methyltertiarvbutyl ether reactor, and another part Fatty Alcohol(C12-C14 and C12-C18) then is to be entered in the stabilizer tower by the different feeds mouth.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.
Alcohol in the described catalytic cracking stabilizer tower/hydrocarbon mass ratio (Fatty Alcohol(C12-C14 and C12-C18)/hydro carbons raw material of etherification mass ratio) is 0.1～0.6, tower top temperature is 40～60 ℃, and column bottom temperature is 140～170 ℃, and pressure tower is 0.9～1.7MPa, in the hydro carbons raw material of etherification, weight space velocity is 1.0～20.0h during feeding liquid
-1The conversion zone temperature is determined by the distribution of stabilizer tower natural temperature gradient.
Described Fatty Alcohol(C12-C14 and C12-C18) is selected from one or more in methyl alcohol, ethanol and the propyl alcohol, particular methanol.
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.
Hydro carbons etherification method technical process with the absorption-stabilization system by catalytic cracking combination provided by the invention is described below: the hydro carbons raw material of etherification from pipeline 1 enters pre-methyltertiarvbutyl ether reactor 17 separately, perhaps with after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 2 mixes enter pre-methyltertiarvbutyl ether reactor 17, under pre-catalyst for etherification effect, react, its resultant of reaction without separate through pipeline 3 with enter catalytic cracking stabilizer tower 5 after Fatty Alcohol(C12-C14 and C12-C18) from pipeline 18 mixes, at the conversion zone 6 of catalytic cracking stabilizer tower 5 with the catalyst for etherification contact reacts and separate, the new Fatty Alcohol(C12-C14 and C12-C18) that replenishes enters conversion zone 6 by pipeline 4, contacts with unreacted tertiary carbon alkene and carries out further etherification reaction.The C that catalytic cracking stabilizer tower 5 is separating obtained
4Component is extracted out from the cat head of catalytic cracking stabilizer tower 5 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 5 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.
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 pre-catalyst for etherification or 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.
(3) owing to be provided with pre-methyltertiarvbutyl ether reactor, the present invention can prolong the life cycle of catalyst for etherification, improves the reaction depth of etherification reaction.
The present invention is further illustrated below by embodiment, but content not thereby limiting the invention.
Used pre-methyltertiarvbutyl ether reactor is fixed-bed reactor among the embodiment, and used catalytic cracking distillation tower is a small-sized simulation stabilizer tower device, height 2.0m, conversion zone 0.8m, stripping section 0.6m, rectifying section 0.6m, rectifying section and stripping section filling Raschig ring filler, conversion zone filling catalyst for etherification.Comparative Examples is carried out on same simulation stabilizer tower device, but in the tower rectifying section and stripping section is only arranged, and does not establish conversion zone.
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.
Embodiment 1
The hydro carbons raw material of etherification that present embodiment adopts is the C that contains 20% iso-butylene
4Cut, C
4Cut is in pre-methyltertiarvbutyl ether reactor and catalyst A contact reacts, and its reaction conditions is that temperature of reaction is 130 ℃, and reaction pressure is 1.5MPa, and weight space velocity is 2.0h during feeding liquid
-1, reaction result is isobutene conversion≤1%, diolefine in the resultant of reaction≤100 μ g/g, alkali nitrogen content≤1 μ g/g.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst A contact reacts and carry out fractionation, obtain gaseous fraction, at the bottom of the tower of stabilizer tower, obtain MTBE by the cat head of stabilizer tower.Operational condition is: alcohol/alkene mass ratio is 0.5, and tower top temperature is 40 ℃, and column bottom temperature is 140 ℃, 120 ℃ of conversion zone temperature ins, and pressure tower is 1.5MPa, the trim the top of column ratio is 5, with C
4The cut meter, weight space velocity is 2.0h during feeding liquid
-1, reaction result is a methanol conversion 100%, generates the MTBE selectivity〉and 99%.
Embodiment 2
The hydro carbons raw material of etherification that present embodiment adopts is a liquefied gas, the content of iso-butylene is 15% in the liquefied gas, after liquefied gas and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst DOCP contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.3, temperature of reaction is 100 ℃, reaction pressure is 1.7MPa, and weight space velocity is 6.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, obtain gaseous fraction, at the bottom of the tower of stabilizer tower, obtain MTBE by the cat head of stabilizer tower.Operational condition is: alcohol/alkene mass ratio is 0.4, and tower top temperature is 40 ℃, and column bottom temperature is 140 ℃, 100 ℃ of conversion zone temperature ins, and pressure tower is 1.7MPa, and the trim the top of column ratio is 5, and in liquefied gas, weight space velocity is 2.0h during feeding liquid
-1, reaction result is a methanol conversion 100%, generates the MTBE selectivity〉and 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 160 ℃, 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.
Embodiment 3
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 1 identical with Comparative Examples 1, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst CGP-1 contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.1, temperature of reaction is 120 ℃, reaction pressure is 1.5MPa, and weight space velocity is 2.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.2, and tower top temperature is 50 ℃, and column bottom temperature is 160 ℃, 90 ℃ of conversion zone temperature ins, and pressure tower is 1.5MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 4.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 24 volume % in the stable gasoline of gained, and octane value is 95, compares with Comparative Examples 1, and olefin(e) centent has reduced by 24%, and octane value has improved 7 units.
Embodiment 4
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 1 identical with Comparative Examples 1, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst DOCP contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.1, temperature of reaction is 100 ℃, reaction pressure is 1.5MPa, and weight space velocity is 2.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.2, and tower top temperature is 50 ℃, and column bottom temperature is 160 ℃, 90 ℃ of conversion zone temperature ins, and pressure tower is 1.5MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 4.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 25 volume % in the stable gasoline of gained, and octane value is 95, compares with Comparative Examples 1, and olefin(e) centent has reduced by 23%, and octane value has improved 7 units.
Embodiment 5
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 1 identical with Comparative Examples 1, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst GOR-II contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.2, temperature of reaction is 100 ℃, reaction pressure is 1.5MPa, and weight space velocity is 2.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.3, and tower top temperature is 50 ℃, and column bottom temperature is 160 ℃, 90 ℃ of conversion zone temperature ins, and pressure tower is 1.5MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 6.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 22 volume % in the stable gasoline of gained, and octane value is 95, compares with Comparative Examples 1, and olefin(e) centent has reduced by 26%, and octane value has improved 7 units.
Embodiment 6
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 1 identical with Comparative Examples 1, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst GOR-II contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.2, temperature of reaction is 100 ℃, reaction pressure is 1.5MPa, and weight space velocity is 6.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalytic cracking catalyst GOR-II contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.3, and tower top temperature is 50 ℃, and column bottom temperature is 160 ℃, 90 ℃ of conversion zone temperature ins, and pressure tower is 1.5MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 6.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 35 volume % in the stable gasoline of gained, and octane value is 90, compares with Comparative Examples 1, and olefin(e) centent has reduced by 13%, 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
Embodiment 7
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 2 identical with Comparative Examples 2, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst GOR-II contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.2, temperature of reaction is 130 ℃, reaction pressure is 1.7MPa, and weight space velocity is 5.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.3, and tower top temperature is 40 ℃, and column bottom temperature is 170 ℃, 80 ℃ of conversion zone temperature ins, and pressure tower is 1.7MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 5.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 23 volume % in the stable gasoline of gained, and octane value is 95, compares with Comparative Examples 2, and olefin(e) centent has reduced by 27%, and octane value has improved 7 units.
Embodiment 8
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 2 identical with Comparative Examples 2, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst CGP-1 contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.1, temperature of reaction is 100 ℃, reaction pressure is 1.7MPa, and weight space velocity is 2.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.3, and tower top temperature is 40 ℃, and column bottom temperature is 170 ℃, 80 ℃ of conversion zone temperature ins, and pressure tower is 1.7MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 6.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 22 volume % in the stable gasoline of gained, and octane value is 95, compares with Comparative Examples 2, and olefin(e) centent has reduced by 28%, and octane value has improved 7 units.
Embodiment 9
The used hydro carbons raw material of etherification of present embodiment is the catalytic cracking deethanizing gasoline stocks 2 identical with Comparative Examples 2, after catalytic cracking deethanizing gasoline and the methanol mixed in pre-methyltertiarvbutyl ether reactor and catalytic cracking catalyst DOCP contact reacts, its reaction conditions is that alcohol/hydrocarbon mass ratio is 0.2, temperature of reaction is 120 ℃, reaction pressure is 1.7MPa, and weight space velocity is 18.0h during feeding liquid
-1, 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.
To enter stabilizer tower after the resultant of reaction of above-mentioned gained and the methanol mixed, in conversion zone and catalyst for etherification storng-acid cation exchange resin Amberlyst35 contact reacts and carry out fractionation, cat head by stabilizer tower obtains liquefied gas, obtains containing the stable gasoline of ether compound at the bottom of the tower of stabilizer tower.Operational condition is: alcohol/hydrocarbon mass ratio is 0.3, and tower top temperature is 40 ℃, and column bottom temperature is 170 ℃, 80 ℃ of conversion zone temperature ins, and pressure tower is 1.7MPa, and the trim the top of column ratio is 5, and with the deethanizing gasoline meter, weight space velocity is 18.0h during feeding liquid
-1
Reaction result is that olefin(e) centent is 28 volume % in the stable gasoline of gained, and octane value is 93, compares with Comparative Examples 2, and olefin(e) centent has reduced by 22%, and octane value has improved 5 units.
Claims (12)
1. hydro carbons etherification method with absorption-stabilization system by catalytic cracking combination, enter pre-methyltertiarvbutyl ether reactor after it is characterized in that the hydro carbons raw material of etherification and the Fatty Alcohol(C12-C14 and C12-C18) of choosing wantonly mixing, contact with pre-catalyst for etherification and to react, its resultant of reaction is without separating and entering the catalytic cracking stabilizer tower after Fatty Alcohol(C12-C14 and C12-C18) mixes, in the conversion zone and the catalyst for etherification contact reacts of catalytic cracking stabilizer tower and carry 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 pre-catalyst for etherification and catalyst for etherification are selected from storng-acid cation exchange resin, in molecular sieve catalyst and the heteropolyacid catalyst one or more; At least contain a kind of tertiary carbon alkene in the described hydro carbons raw material of etherification; Be provided with conversion zone and rectifying section and/or stripping section in the described catalytic cracking stabilizer tower, rectifying section is positioned at the top of conversion zone, and stripping section is positioned at the below of conversion zone; Described Fatty Alcohol(C12-C14 and C12-C18) is selected from one or more in methyl alcohol, ethanol and the propyl alcohol.
2. in accordance with the method for claim 1, 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.
3. in accordance with the method for claim 1, it is characterized in that described pre-methyltertiarvbutyl ether reactor is fixed-bed reactor and/or fluidized-bed reactor.
4. in accordance with the method for claim 1, 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. in accordance with the method for claim 1, the conversion zone that it is characterized in that described catalytic cracking stabilizer tower is provided with 2～6 Fatty Alcohol(C12-C14 and C12-C18) opening for feeds.
6. in accordance with the method for claim 1, it is characterized in that alcohol in the described catalytic cracking stabilizer tower/hydrocarbon mass ratio is 0.1～0.6, tower top temperature is 40～60 ℃, column bottom temperature is 140～170 ℃, pressure tower is 0.9～1.7MPa, in the hydro carbons raw material of etherification, weight space velocity is 1.0～20.0h during feeding liquid
-1
7. in accordance with the method for claim 1, it is characterized in that described molecular sieve catalyst comprises molecular sieve, inorganic oxide and optional clay, each components contents is respectively: molecular sieve 10～50 heavy %, inorganic oxide 5～90 heavy %, clay 0～70 heavy %.
8. in accordance with the method for claim 7, 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.
9. in accordance with the method for claim 8, 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.
10. in accordance with the method for claim 9, 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.
11. in accordance with the method for claim 7, described inorganic oxide is selected from silicon-dioxide and/or aluminium sesquioxide.
12. in accordance with the method for claim 7, 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046549A (en) * | 1989-04-22 | 1990-10-31 | 抚顺石油学院 | The etherification technology method of olefine contained gasoline |
| US4990712A (en) * | 1990-05-18 | 1991-02-05 | Mobil Oil Corporation | Integrated cracking, etherification and olefin upgrading process |
| US20040186331A1 (en) * | 2002-12-23 | 2004-09-23 | Patrick Briot | Process for transforming hydrocarbons into a fraction having an improved octane number and a fraction with a high cetane index |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046549A (en) * | 1989-04-22 | 1990-10-31 | 抚顺石油学院 | The etherification technology method of olefine contained gasoline |
| US4990712A (en) * | 1990-05-18 | 1991-02-05 | Mobil Oil Corporation | Integrated cracking, etherification and olefin upgrading process |
| US20040186331A1 (en) * | 2002-12-23 | 2004-09-23 | Patrick Briot | Process for transforming hydrocarbons into a fraction having an improved octane number and a fraction with a high cetane index |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Volume: 27 |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Page: The title page Volume: 27 |
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Free format text: CORRECT: PATENTEE; ADDRESS; CO-PATENTEE; FROM: SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING;100083 NO. 18, XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING TO: CHINA PETROCHEMICAL CO., LTD.;100029 NO. 6-A, HUIXIN EAST STREET, CHAOYANG DISTRICT, BEIJING; SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING |