CN109517623A - A kind of integrated processes of light FCC gasoline etherificate and isomerisation of olefin - Google Patents
A kind of integrated processes of light FCC gasoline etherificate and isomerisation of olefin Download PDFInfo
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- CN109517623A CN109517623A CN201710850443.3A CN201710850443A CN109517623A CN 109517623 A CN109517623 A CN 109517623A CN 201710850443 A CN201710850443 A CN 201710850443A CN 109517623 A CN109517623 A CN 109517623A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The present invention relates to a kind of integrated processes of light FCC gasoline etherificate and isomerisation of olefin, it includes the following steps: A, by the mixture of light FCC gasoline raw material and excessive methanol successively through the first methyltertiarvbutyl ether reactor and the second methyltertiarvbutyl ether reactor handle it is anti-after material after catalytic rectifying tower is handled, the component as etherified gasoline product is obtained from catalytic rectifying tower tower bottom, the component comprising light dydrocarbon hydro carbons and unreacted methanol is obtained from catalytic distillation column overhead；B obtains oily phase and water phase after comprising the processing of the first water scrubber of group lease making of light dydrocarbon hydro carbons and unreacted methanol；C, the isomerization product that the oil is mutually handled through isomerization reactor obtain etherification product after supplement methyltertiarvbutyl ether reactor processing；D handles etherification product through the second water scrubber, respectively obtains oil phase and water phase as etherified gasoline product.
Description
Technical field
The invention belongs to light FCC gasoline etherificates and isomerisation of olefin technical field, and in particular to a kind of catalytic cracking
The integrated processes of Etherification of Light FCC Gasoline and isomerisation of olefin.
Background technique
Catalytic cracking is one of the main technique of petroleum secondary operation, can produce gasoline, diesel oil and portion gas hydro carbons.
Carbon four therein, C5 fraction are comprehensively utilized, value-added content of product is improved, farthest increasing economic benefit is to grind
One of hot spot studied carefully, and many techniques related to this are developed, wherein Etherification of Light FCC Gasoline is using relatively broad.
Etherification of Light FCC Gasoline technology is mainly by seven active olefin of light dydrocarbon-carbon in light FCC gasoline in catalyst action
Lower and methanol carries out etherification reaction and produces ether compound, can not only reduce the olefin(e) centent in gasoline, gasoline also can be improved
Octane number and reduce vapour pressure, enhance its stability, benefit is fairly obvious.And in light petrol in addition to isomeric olefine, also contain
The normal olefine of a certain amount of not etherification activity, is etherified, not only after being translated into isomeric olefine by isomerization technique
The yield of high-knock rating gasoline is increased, and further reduced the olefin(e) centent of gasoline, remarkable in economical benefits.
The process integration of Etherification of Light FCC Gasoline and olefin isomerization mainly has DET technique and the CDTECH company of Snam company at present
CDEthers technique.DET technique (technical progress of light FCC gasoline etherification technology, petrochemical industry, 2008) shares three
Section methyltertiarvbutyl ether reactor, it is anti-after light dydrocarbon be separately separated out after enter alkane separation tower, pass through selective vapor absorbing process point
From for pentane and amylene, pentane is incorporated in depentanizer product, and amylene enters isomerization reactor, and the iso-amylene of production returns to ether
Change reactor.This technique is to the good separating effect of n-pentene, but separating technology is complicated, operating cost is higher, and not methanol
Workshop section is separated and recovered, therefore the methanol in raw material must be strictly controlled, this affects the conversion ratio of etherification of olefine, improves simultaneously
The difficulty of operation.
CDEthers technique (Integrated process for the production of tame [P] .US
5792891) it is equipped with three sections of reactors and a catalyst rectifying column altogether, etherification conversion rate is improved using the excessive method of methanol,
Therefore it is equipped with Methanol Recovery workshop section.Methanol is steamed from catalytic distillation column overhead to enter after third reactor with light dydrocarbon azeotropic mixture
Methanol extraction tower enters isomerization reactor after separation methanol is washed with water.It is generated due to containing third reactor in overhead product
Tert amyl methyl ether(TAME) (TAME), after this overhead stream is directly entered isomerization reactor, TAME can be cracked, and not only be generated
The by-products such as dimethyl ether, and the methanol being cracked to form can also make catalyst poisoning, influence catalyst service life.In addition,
The product circulation of isomerization reactor is returned the entrance of methyltertiarvbutyl ether reactor by this technique, since isomeric olefine content is few in product, greatly
The alkane of amount recycles in a device, to increase the energy consumption and machine utilization of methyltertiarvbutyl ether reactor.
Therefore, presently, there are the problem of be to be badly in need of researching and developing a kind of light FCC gasoline etherificate and isomerisation of olefin
Integrated processes.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of light vapour of catalytic cracking
The integrated processes of oil etherificate and isomerisation of olefin.The method of the present invention passes through the catalytic distillation to light FCC gasoline ether-based device
The improvement of tower makes the conversion ratio of isomeric olefine reach 95% or more, thus reduce influence of the reaction balance to isomerization reaction,
And improve the separating effect of catalytic rectifying tower；Simultaneously by the way that water scrubber and isomerization reaction is arranged in process flow interlude
Unit not only solved the problems, such as that a large amount of alkane circulation bring energy consumptions increased, but also can improve the utilization rate for supplementing methyltertiarvbutyl ether reactor, from
And it further increases methanol consumption amount and increases the yield of etherified gasoline product, and improve device economic benefit.
For this purpose, the present invention provides a kind of integrated processes of light FCC gasoline etherificate and isomerisation of olefin comprising
Following steps:
A, by the mixture of light FCC gasoline raw material and excessive methanol successively through the first methyltertiarvbutyl ether reactor and the second ether
The anti-rear material that change reactor for treatment obtains is obtained from catalytic rectifying tower tower bottom as etherified gasoline after catalytic rectifying tower is handled
The component of product obtains the component comprising light dydrocarbon hydro carbons and unreacted methanol from catalytic distillation column overhead；
B, the first water of group lease making comprising light dydrocarbon hydro carbons and unreacted methanol that will be obtained from catalytic distillation column overhead
After washing tower processing, oily phase is obtained from the first washing column overhead, obtains water phase from the first water scrubber tower bottom；
C, the isomerization product that the oil obtained from the first washing column overhead is mutually handled through isomerization reactor is through mending
After filling methyltertiarvbutyl ether reactor processing, etherification product is obtained；
D handles etherification product through the second water scrubber, obtains the oil as etherified gasoline product from the second washing column overhead
Phase obtains water phase from the second water scrubber tower bottom.
According to the method for the present invention, the light FCC gasoline raw material includes seven hydro carbons of light dydrocarbon hydro carbons, six hydro carbons of carbon and carbon.
Term " hydro carbons " of the present invention refers to alkane and alkene.
In certain embodiments of the present invention, in step, the alkene in the light FCC gasoline raw material and institute
The mass ratio for stating methanol is 1:(1.2-3.0), preferably 1:(1.4-2.0).
According to the method for the present invention, in step, light FCC gasoline raw material is etherified in the first methyltertiarvbutyl ether reactor and second
The etherification reaction of seven alkene of etherification reaction and a small amount of carbon six and carbon of part C_5 olefins mainly occurs in reactor.Cause
This, light FCC gasoline raw material is after the first methyltertiarvbutyl ether reactor and the processing of the second methyltertiarvbutyl ether reactor, from the second methyltertiarvbutyl ether reactor
The anti-rear material (material after reacting) that bottom obtains is comprising tert amyl methyl ether(TAME), unreacted hydrocarbon and methanol；Wherein, not
The hydrocarbon of reaction includes seven hydro carbons of unreacted light dydrocarbon hydro carbons, six hydro carbons of unreacted carbon and unreacted carbon.
According to the method for the present invention, in step, by the anti-rear material obtained from the second methyltertiarvbutyl ether reactor bottom through catalysis essence
Tower processing is evaporated, by improving the loaded catalyst of catalytic rectifying tower and adjusting reflux ratio, the conversion ratio of etherification reaction is improved
To 95% or more.
In certain embodiments of the present invention, in step, the reflux ratio of the catalytic rectifying tower is 0.5-2.5, excellent
It is selected as 1.5-1.8.
According to the method for the present invention, in step, the anti-rear material obtained from the second methyltertiarvbutyl ether reactor bottom is through catalytic distillation
After tower processing, the component as etherified gasoline product is obtained from catalytic rectifying tower tower bottom, is included from catalytic distillation column overhead
The component of light dydrocarbon hydro carbons and unreacted methanol.The component as etherified gasoline product includes tert amyl methyl ether(TAME)
(TAME) and seven hydro carbons of six hydro carbons of carbon and carbon.The content of tert amyl methyl ether(TAME) is small from the component that catalytic distillation column overhead obtains
In 100ppm.
According to the method for the present invention, in stepb, it will be obtained from catalytic distillation column overhead comprising carbon using the first water scrubber
The separation of the component of five hydro carbons and unreacted methanol obtains oily phase from the first washing column overhead, obtains from the first water scrubber tower bottom
To water phase.The oil mutually includes light dydrocarbon hydro carbons, and wherein the content of methanol is less than 100ppm.The water phase includes methanol and water
Mixture.After the processing of the first water scrubber, so that the oily Xiang Zhongjia comprising light dydrocarbon hydro carbons obtained from the first washing column overhead
The content of alcohol substantially reduces, to prevent the poisoning effect of the catalyst in the isomerization reactor to downstream.
In certain embodiments of the present invention, in stepb, the oil is mutually 1:(3- with the volume ratio of the water phase
4)。
According to the method for the present invention, in step C, the oil comprising light dydrocarbon hydro carbons obtained from the first washing column overhead is mutually passed through
Isomerization reactor processing, in isomerization reactor, the normal olefine in light dydrocarbon hydro carbons is isomerized to etherification activity
Isomeric olefine after obtain isomerization product.After isomerization reaction, the isomerization product (group i.e. after isomerization reaction
Point) in isomery C_5 olefins content compared with enter isomerization reactor component (component i.e. before isomerization reaction) in isomery carbon
The content of five alkene increases 8%-10%.
In certain embodiments of the present invention, the reaction temperature in the isomerization reactor is 290-360 DEG C, reaction
Pressure is 0.01-0.2MPa.
According to the method for the present invention, in step C, during isomerization product enters supplement methyltertiarvbutyl ether reactor, simultaneously
It is passed through methanol, the alkene (isomeric olefine) in supplement methyltertiarvbutyl ether reactor, isomerization product occurs etherification reaction with methanol and obtains
Etherification product.
In certain embodiments of the present invention, the molar ratio of the alkene in the isomerization product and methanol is 1:
(1.5-2)。
According to the method for the present invention, in step D, etherification product is handled using the second water scrubber, from the second washing column overhead
The oily phase as etherified gasoline product comprising seven hydro carbons of tert amyl methyl ether(TAME), six hydro carbons of carbon and carbon is obtained, from the second water scrubber
Tower bottom obtains the water phase of the mixture comprising methanol and water.
In certain embodiments of the present invention, in step D, the oil is mutually 1:(2- with the volume ratio of the water phase
3)。
The method of the present invention include thes steps that carrying out separating E with the water phase of the mixture of water comprising methanol, i.e., will be from
After the water phase that one water scrubber and the second water scrubber tower bottom are isolated enters methanol rectifying tower processing, it will be obtained from methanol rectification column overhead
The methanol arrived returns to the first methyltertiarvbutyl ether reactor or methyl tertiary butyl ether(MTBE) synthesizer, and the water obtained from methanol rectifying tower tower bottom is returned
Return the first water scrubber or the second water scrubber.
The process integration of light FCC gasoline etherificate provided by the invention and isomerisation of olefin improves etherification reaction and turns
Rate reduces the influence that isomeric olefine balances olefin isomerization, extends the service life of isomerization catalyst, and
And improve the separating effect of tower；Simultaneously by the way that water scrubber and isomerization reaction unit is arranged in process flow interlude, both solved
A large amount of alkane circulation bring energy consumptions of having determined increase problem, and can improve the utilization rate of supplement methyltertiarvbutyl ether reactor, thus further
It improves methanol consumption amount and increases the yield of etherified gasoline product, improve device economic benefit.
Detailed description of the invention
It is next with reference to the accompanying drawing that invention is further described in detail.
Fig. 1 is the process flow chart according to certain specific embodiments of the invention.In figure, the meaning of appended drawing reference is such as
Under:
1- light FCC gasoline raw material；The first methyltertiarvbutyl ether reactor of R1-；The second methyltertiarvbutyl ether reactor of R2-；T1- catalytic distillation
Tower；The component comprising light dydrocarbon hydro carbons and unreacted methanol that 2- is obtained from catalytic distillation column overhead；3- is from catalytic rectifying tower tower
The component as etherified gasoline product that bottom obtains；The first water scrubber of T2-；What 4- was obtained from the first washing column overhead includes light dydrocarbon
The oily phase of hydro carbons；The water phase for the mixture comprising methanol and water that 5- is obtained from the first water scrubber tower bottom；R3- isomerization reaction
Device；6- isomerization product；R4- supplements methyltertiarvbutyl ether reactor；7- etherification product；The second water scrubber of T3-；8- washes column overhead from second
The obtained oily phase as etherified gasoline product；The water for the mixture comprising methanol and water that 9- is obtained from the second water scrubber tower bottom
Phase.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment and attached drawing, the present invention will be described in detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention.
As previously mentioned, in the integrated processes of existing light FCC gasoline etherificate and isomerisation of olefin, isomerization is anti-
It answers the product circulation of device to return the entrance of methyltertiarvbutyl ether reactor, considerably increases the energy consumption and machine utilization of methyltertiarvbutyl ether reactor.In view of upper
Problem is stated, the present inventor has found after study, and by being adjusted to catalytic rectifying tower operating parameter, alkene can be improved
Etherification conversion rate, reduce the influence of isomeric olefine in isomerate feeds to reaction balance, while improving the separation effect of tower
Fruit.In this way under the premise of isomerization product does not recycle, isomerisation conversion is improved, increases the production of etherified benzine product
Amount.The present invention is based on what above-mentioned discovery was made.
Fig. 1 shows some tools of light FCC gasoline etherificate and the integrated processes of isomerisation of olefin according to the present invention
The process flow chart of body embodiment.As shown in Figure 1, (it is mainly formed light FCC gasoline raw material 1 are as follows: isopentane
35wt%, 2-methyl-1-butene alkene 6.5wt%, pentane 7.5wt%, trans- 2- amylene 8.0wt%, cis- 2- amylene 3.2wt%,
- 2 butylene 16.7wt% of 2- methyl) and methanol mixing after, pass sequentially through the first methyltertiarvbutyl ether reactor R1 and the second methyltertiarvbutyl ether reactor R2
Etherification reaction is carried out, to guarantee etherification conversion rate, methanol keeps excessive state, so that the alkene in light FCC gasoline raw material 1
The mass ratio of hydrocarbon and methanol is 1:(1.2-3.0), wherein the conversion ratio of iso-amylene is 60%-65%, and the conversion ratio of dissident's alkene is
32%-37%.The anti-rear material obtained from the second bottom methyltertiarvbutyl ether reactor R2 enters catalytic rectifying tower T1, and the reflux ratio of tower is
1.5-1.8, the conversion ratio of isomery C_5 olefins are 95%；Catalytic rectifying tower tower bottom is isolated comprising seven hydrocarbon of TAME, carbon six and carbon
The mixture 3 of class goes out device as etherified gasoline product, and tower top is isolated comprising C_5 olefins and the entrance of unreacted methanol 2
First water scrubber T2.Wherein, the content of tert amyl methyl ether(TAME) is less than 100ppm in the component 2 that tower top is isolated.Include light dydrocarbon alkene
The component 2 of hydrocarbon and unreacted methanol, with as the water counter current contacting of extractant, washes away methanol therein in the first water scrubber T2,
The oily phase 4 separated from tower top is used as isomerization reactor R3 raw material, wherein the content of methanol is less than 100ppm in oily phase 4.
Enter after being separated containing methanol and the water phase 5 of the mixture of water from the first water scrubber T2 tower bottom methanol rectifying tower tower carry out methanol and
The separation of water.The molar ratio of the oily phase 4 and water phase 5 that obtain from the first water scrubber T2 is 1:(3-4).In isomerization reactor R3
In, reaction temperature is 290-360 DEG C, reaction pressure 0.01-0.2MPa, and the normal olefine in oily phase 4, which is converted into, has etherificate
Active isomeric olefine, the conversion ratio of n-pentene are 80%, and the selectivity of iso-amylene is 90%.Isomerization product 6 and methanol into
Enter to supplement methyltertiarvbutyl ether reactor R4, the molar ratio of the alkene (isomeric olefine) in isomerization product and methanol is 1:(1.5-2).Isomery
Alkene is reacted with methanol generates the etherification product 7 comprising TAME.Etherification product 7 subsequently enters the second water scrubber T3, again with work
For the water counter current contacting of extractant, the conduct etherified gasoline product obtained after methanol therein from the second water scrubber T3 tower top is washed away
Oily phase 8 go out device, obtain the water phase 9 of the mixture comprising methanol and water from the second water scrubber T3 tower bottom.From the second water scrubber
The molar ratio of oily phase 8 and water phase 9 that T3 is obtained is 1:(1-2).Water phase 9 enters the separation that methanol rectifying tower carries out first alcohol and water.
Light FCC gasoline etherificate provided by the invention and the integrated processes of isomerisation of olefin meet isomerization reaction
Requirement to alcohol, ethers impurity content in raw material ensure that the performance of isomerization reaction, reach the regeneration period of catalyst
By 40 days or more, the yield of etherified benzine product, which (is free of isomerization reactor) compared with the conventional method, can be improved 8%-
10%；A water scrubber is merely added compared with the existing methods simultaneously, and existing supplement methyltertiarvbutyl ether reactor is utilized, avoids
Isomerization product needs the case where being recycled back to methyltertiarvbutyl ether reactor in existing method, and energy saving has considerable 30% or more
Economic benefit.
Embodiment
Embodiment 1
Process flow such as Fig. 1 of light FCC gasoline etherificate and the integrated processes of isomerisation of olefin provided in this embodiment
It is shown.
Light FCC gasoline raw material 1 (it is mainly formed are as follows: isopentane 35wt%, 2-methyl-1-butene alkene 6.5wt%, just
Pentane 7.5wt%, trans- 2- amylene 8.0wt%, cis- -2 butylene 16.7wt% of 2- amylene 3.2wt%, 2- methyl) and methanol mixing
Afterwards, it passes sequentially through the first methyltertiarvbutyl ether reactor R1 and the second methyltertiarvbutyl ether reactor R2 and carries out etherification reaction, to guarantee etherification conversion rate, first
Alcohol keeps excessive state, so that the mass ratio of alkene and methanol in light FCC gasoline raw material 1 is 1:1.2, wherein isoamyl
The conversion ratio of alkene is 60%, and the conversion ratio of dissident's alkene is 32%.Obtained from the second bottom methyltertiarvbutyl ether reactor R2 it is anti-after material into
Enter catalytic rectifying tower T1, the reflux ratio of tower is 1.6, and the conversion ratio of isomery C_5 olefins is 95%；The separation of catalytic rectifying tower tower bottom
Out include the mixture 3 of seven hydro carbons of TAME, carbon six and carbon, goes out device as etherified gasoline product, tower top is isolated comprising light dydrocarbon
Alkene and unreacted methanol 2 enter the first water scrubber T2.Wherein, tert amyl methyl ether(TAME) contains in the component 2 that tower top is isolated
Amount is less than 100ppm.Component 2 comprising C_5 olefins and unreacted methanol is in the first water scrubber T2 and as the water of extractant
Counter current contacting washes away methanol therein, and the oily phase 4 separated from tower top is used as isomerization reactor R3 raw material, wherein oily phase
The content of methanol is less than 100ppm in 4.It is separated from the first water scrubber T2 tower bottom containing methanol with the water phase 5 of the mixture of water laggard
Enter the separation that methanol rectifying tower tower carries out first alcohol and water.The molar ratio of the oily phase 4 and water phase 5 that obtain from the first water scrubber T2 is 1:
3.5.In isomerization reactor R3, reaction temperature is 290 DEG C, reaction pressure 0.01-0.2MPa, the positive structure alkene in oily phase 4
Hydrocarbon is converted into the isomeric olefine with etherification activity, and the conversion ratio of n-pentene is 80%, and the selectivity of iso-amylene is 90%.Isomery
Change product 6 and methanol enters supplement methyltertiarvbutyl ether reactor R4, the molar ratio of alkene (isomeric olefine) and methanol in isomerization product
For 1:1.5.Isomeric olefine is reacted with methanol generates the etherification product 7 comprising TAME.Etherification product 7 subsequently enters the second water scrubber
T3 washes away the conduct obtained after methanol therein from the second water scrubber T3 tower top again with the water counter current contacting as extractant
The oily phase 8 of etherified gasoline product goes out device, obtains the water phase 9 of the mixture comprising methanol and water from the second water scrubber T3 tower bottom.
The molar ratio of the oily phase 8 and water phase 9 that obtain from the second water scrubber T3 is 1:1.Water phase 9 enters methanol rectifying tower and carries out first alcohol and water
Separation.The yield of etherified benzine is 214900 tons/year.
Embodiment 2
Process flow such as Fig. 1 of light FCC gasoline etherificate and the integrated processes of isomerisation of olefin provided in this embodiment
It is shown.
Light FCC gasoline raw material 1 (it is mainly formed are as follows: isopentane 35wt%, 2-methyl-1-butene alkene 6.5wt%, just
Pentane 7.5wt%, trans- 2- amylene 8.0wt%, cis- -2 butylene 16.7wt% of 2- amylene 3.2wt%, 2- methyl) and methanol mixing
Afterwards, it passes sequentially through the first methyltertiarvbutyl ether reactor R1 and the second methyltertiarvbutyl ether reactor R2 and carries out etherification reaction, to guarantee etherification conversion rate, first
Alcohol keeps excessive state, so that the mass ratio of alkene and methanol in light FCC gasoline raw material 1 is 1:3.0, wherein isoamyl
The conversion ratio of alkene is 65%, and the conversion ratio of dissident's alkene is 37%.Obtained from the second bottom methyltertiarvbutyl ether reactor R2 it is anti-after material into
Enter catalytic rectifying tower T1, the reflux ratio of tower is 1.6, and the conversion ratio of isomery C_5 olefins is 95%；The separation of catalytic rectifying tower tower bottom
Out include the mixture 3 of seven hydro carbons of TAME, carbon six and carbon, goes out device as etherified gasoline product, tower top is isolated comprising light dydrocarbon
Alkene and unreacted methanol 2 enter the first water scrubber T2.Wherein, tert amyl methyl ether(TAME) contains in the component 2 that tower top is isolated
Amount is less than 100ppm.Component 2 comprising C_5 olefins and unreacted methanol is in the first water scrubber T2 and as the water of extractant
Counter current contacting washes away methanol therein, and the oily phase 4 separated from tower top is used as isomerization reactor R3 raw material, wherein oily phase
The content of methanol is less than 100ppm in 4.It is separated from the first water scrubber T2 tower bottom containing methanol with the water phase 5 of the mixture of water laggard
Enter the separation that methanol rectifying tower tower carries out first alcohol and water.The molar ratio of the oily phase 4 and water phase 5 that obtain from the first water scrubber T2 is 1:
3.5.In isomerization reactor R3, reaction temperature is 290 DEG C, reaction pressure 0.01-0.2MPa, the positive structure alkene in oily phase 4
Hydrocarbon is converted into the isomeric olefine with etherification activity, and the conversion ratio of n-pentene is 80%, and the selectivity of iso-amylene is 90%.Isomery
Change product 6 and methanol enters supplement methyltertiarvbutyl ether reactor R4, the molar ratio of alkene (isomeric olefine) and methanol in isomerization product
For 1:2.Isomeric olefine is reacted with methanol generates the etherification product 7 comprising TAME.Etherification product 7 subsequently enters the second water scrubber
T3 washes away the conduct obtained after methanol therein from the second water scrubber T3 tower top again with the water counter current contacting as extractant
The oily phase 8 of etherified gasoline product goes out device, obtains the water phase 9 of the mixture comprising methanol and water from the second water scrubber T3 tower bottom.
The molar ratio of the oily phase 8 and water phase 9 that obtain from the second water scrubber T3 is 1:2.Water phase 9 enters methanol rectifying tower and carries out first alcohol and water
Separation.The yield of etherified benzine is 217900 tons/year.
Comparative example 1
Using prior art process, i.e., isomerization reactor R3 and the second water scrubber T3 are not set, light FCC gasoline is former
(it is mainly formed material 1 are as follows: isopentane 35wt%, 2-methyl-1-butene alkene 6.5wt%, pentane 7.5wt%, trans- 2- amylene
8.0wt%, cis- -2 butylene 16.7wt% of 2- amylene 3.2wt%, 2- methyl) and methanol mixing after, it is anti-to pass sequentially through the first etherificate
Device R1 and the second methyltertiarvbutyl ether reactor R2 is answered to carry out etherification reaction, the quality of alkene and methanol in light FCC gasoline raw material 1
Than for 1:3.0, wherein the conversion ratio of iso-amylene is 65%, and the conversion ratio of dissident's alkene is 37%.From the second bottom methyltertiarvbutyl ether reactor R2
The anti-rear material that portion obtains enters catalytic rectifying tower T1, and the reflux ratio of tower is 1.6, and the conversion ratio of isomery C_5 olefins is 95%；
Catalytic rectifying tower tower bottom isolates the mixture 3 comprising seven hydro carbons of TAME, carbon six and carbon, goes out device as etherified gasoline product,
Tower top, which is isolated, enters the first water scrubber T2 comprising C_5 olefins and unreacted methanol 2.Wherein, the component 2 that tower top is isolated
The content of middle tert amyl methyl ether(TAME) is less than 100ppm.Component 2 comprising C_5 olefins and unreacted methanol is in the first water scrubber
T2 and the water counter current contacting as extractant, wash away methanol therein, the oily phase 4 separated from tower top and catalytic rectifying tower tower
Substrate material converge after collectively as etherified gasoline product.The yield of etherified benzine is 199000 tons/year.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (11)
1. a kind of integrated processes of light FCC gasoline etherificate and isomerisation of olefin comprising following steps:
A is successively anti-through the first methyltertiarvbutyl ether reactor and the second etherificate by the mixture of light FCC gasoline raw material and excessive methanol
The anti-rear material for answering device to handle is obtained from catalytic rectifying tower tower bottom as etherified gasoline product after catalytic rectifying tower is handled
Component, obtain the component comprising light dydrocarbon hydro carbons and unreacted methanol from catalytic distillation column overhead；
B, the first water scrubber of group lease making comprising light dydrocarbon hydro carbons and unreacted methanol that will be obtained from catalytic distillation column overhead
After processing, oily phase is obtained from the first washing column overhead, obtains water phase from the first water scrubber tower bottom；
C, the isomerization product that the oil obtained from the first washing column overhead is mutually handled through isomerization reactor is through supplementing ether
After changing reactor for treatment, etherification product is obtained；
D handles etherification product through the second water scrubber, obtains the oily phase as etherified gasoline product from the second washing column overhead,
Water phase is obtained from the second water scrubber tower bottom.
2. the method according to claim 1, wherein the light FCC gasoline raw material include light dydrocarbon hydro carbons,
Seven hydro carbons of six hydro carbons of carbon and carbon.
3. method according to claim 1 or 2, which is characterized in that in step, the light FCC gasoline raw material
In alkene and the methanol mass ratio be 1:(1.2-3.0).
4. method described in any one of -3 according to claim 1, which is characterized in that in step, the catalytic rectifying tower
Reflux ratio be 0.5-2.5, preferably 1.5-1.8.
5. method described in any one of -4 according to claim 1, which is characterized in that in step, from catalytic rectifying tower tower
The content for pushing up tert amyl methyl ether(TAME) in obtained component is less than 100ppm.
6. method described in any one of -5 according to claim 1, which is characterized in that in stepb, described from the first washing
The oil that column overhead obtains mutually includes light dydrocarbon hydro carbons；
The oil is mutually 1:(3-4 with the volume ratio of the water phase)；It is preferred that the content of methanol is less than 100ppm in the oil phase.
7. method described in any one of -6 according to claim 1, which is characterized in that in step C, be etherified in the supplement
In reactor, alkene and methanol in the isomerization product react to obtain etherification product；It is preferred that the isomerization product
In alkene and methanol molar ratio be 1:(1.5-2).
8. method according to any one of claims 1-7, which is characterized in that in step C, the isomerization reaction
Reaction temperature in device is 290-360 DEG C, reaction pressure 0.01-0.2MPa.
9. method described in any one of -8 according to claim 1, which is characterized in that in step D, it is described oil mutually with it is described
The volume ratio of water phase is 1:(2-3).
10. method described in any one of -9 according to claim 1, which is characterized in that described as etherified gasoline product
Component includes seven hydro carbons of tert amyl methyl ether(TAME), six hydro carbons of carbon and carbon.
11. method described in any one of -10 according to claim 1, which is characterized in that the water phase is the mixed of methanol and water
Close object；It is preferred that the method also includes step E, it, will be from methanol rectification column overhead by the water phase after methanol rectifying tower is handled
Obtained methanol returns to the first methyltertiarvbutyl ether reactor or methyl tertiary butyl ether(MTBE) synthesizer, the water that will be obtained from methanol rectifying tower tower bottom
Return to the first water scrubber or the second water scrubber.
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