CN85105107A - Improve the complete processing of olefinic gasolines with etherification - Google Patents
Improve the complete processing of olefinic gasolines with etherification Download PDFInfo
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- CN85105107A CN85105107A CN85105107.3A CN85105107A CN85105107A CN 85105107 A CN85105107 A CN 85105107A CN 85105107 A CN85105107 A CN 85105107A CN 85105107 A CN85105107 A CN 85105107A
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Abstract
Involved in the present invention is one utilize etherification to improve to contain C
5Hydro carbons but do not contain C
4The complete processing of hydrocarbon olefin gasolines.The feature of this technology is: special alkene in the charging and methyl alcohol reaction (1,2); With water extraction (3) reaction effluent, contain the water and the hydrocarbon phase that contains most of ether that is generated of most of unreacted methanol with separation.Then water is imported distillation zone (4), in the distillation zone, water separates with methyl alcohol and is recycled to extract distinguishes (3), and methyl alcohol then is recycled to etherification zone (1 and 2).
Description
In the composition of gasoline pool, constituted the major portion of motor gasoline by cracking equipment (viscosity breaking equipment or the bright burnt equipment) olefin gasolines that flows into.Yet generally the octane value of these olefin gasolines is lower, and inciting somebody to action wherein with methyl alcohol, some etherification of olefine can increase its octane value.In fact, contain the easily special alkene of generation methyl ether in the light fraction of these olefin gasolines with alcohols (as methyl alcohol) reaction, as isopentene, dissident's alkene and iso-heptene.
This etherification reaction generally carries out in the presence of acid catalyst, particularly ion-exchange resin catalyst, for example sulfonate resin.
In the presence of sulfonate resin, handling olefin gasolines with methyl alcohol can increase its octane value and reduce the content of its alkene (mainly being special alkene), thereby might improve the grade of gasoline and become premium motor fuel and do not have the problem that methyl alcohol is directly imported in the gasoline to be produced with methyl alcohol.In fact, free methanol has increased the vapour pressure of gasoline, can cause being separated when water imports storage tank and dispensing loop.
Just because of above-mentioned last reason, regulation does not allow to import methyl alcohol in gasoline in the rule of some major countries, unless there is the solubilizing agent of eliminating lamination problem to exist.
Reaction between methyl alcohol and the special alkene is the equilibrated reaction, therefore, generally is difficult to reach the transformation efficiency near 100%.The molecular weight of alkene is high more, and special conversion of olefines rate is just low more.
Thus, concerning the conversion of iso-butylene, only need it is passed through catalyzer, conversion for isobutene can be up to 93-98%, and the transformation efficiency of isopentene, described in French Patent 2411881, under the condition that is similar to production methyl-tertiary butyl ether (MTBE), the highest 50-60% that is about.This patent proposes, and the light fraction that contains the unreacted isopentene that a part of reactor effluent is distilled the back gained is recycled in the reactor, under above-mentioned same operational condition, might obtain about 70% maximum conversion rate.Need expensive viewpoint from distillation procedure, doing like this is rational economically.
Do not consider in the above-mentioned process flow sheet and remove the excessive methanol that remains in the reactor effluent that therefore, these excessive methyl alcohol major parts are present in the gasoline with unbound state.
In order to remove C fully
4And C
5Excessive methanol after the special alkene mixture etherificate in the gained mixture, United States Patent (USP) 4204077 proposes to adopt solvent such as ethylene glycol to come the extraction reactor effluent to remove methyl alcohol wherein.
The author of this patent thinks that ethylene glycol is better than water, and in the process of extracting methyl alcohol, water can be taken away a part of ether in the reactor effluent.
The objective of the invention is to produce high-octane C by the olefines fraction
+ 5The hydrocarbon fraction.
A kind of alkene fraction contains the hydrocarbon that per molecule is 5 and 5 above carbon atoms, does not contain 4 a large amount of carbon atom hydrocarbon, and promptly the content of 4 carbon atom hydrocarbon is less than 5%(by weight), preferably less than 1% of fraction gross weight.The complete processing that is used for improving above-mentioned alkene fraction may further comprise the steps:
A) olefin gasolines is added etherification zone, react at this fraction of etherification zone and methyl alcohol and obtain containing the effluent of tertiary amyl methyl ether.
B) effluent with above-mentioned a) step gained adds the extraction district, and water extracts most of at least unreacted methanol in extracting the district, and reclaims the part of having removed most of methyl alcohol at least and having contained most of tert amyl methyl ether.
C) fractionation is by b) the step gained contain aqueous extract obtaining methanol content and increase and the fraction (α) that water-content has reduced, and methanol content reduces and fraction (β) that water-content has increased.
D) be recycled to etherification zone to the above-mentioned fraction that has increased methanol content of a major general part, be recycled to the above-mentioned fraction that has increased water-content of major general's part simultaneously and extract the district.
This complete processing can improve the grade of alkene fraction, for example can improve the grade of alkene petroleum naphtha, as long as this petroleum naphtha does not contain a large amount of C
4Hydro carbons.These olefines fractions can contain C
5-C
7The petroleum naphtha of fraction, particularly catalytic cracking, this petroleum naphtha mainly contains C
5, C
6And C
7Hydro carbons, particularly isopentene, for example 2-methyl-1-butene alkene, the 2-methyl-2-butene, with dissident's alkene, for example 2,3-dimethyl-1-butylene, 2,3-dimethyl-2-butylene, 2-methyl-2-amylene, 2-Methyl-1-pentene, 3-methyl-2-amylene and 2-ethyl-1-butylene, and special heptene.
In order to reach sufficiently high transformation efficiency, the consumption of methyl alcohol is the ingress at etherification zone, but the mole ratio of the alkene of methyl alcohol and etherificate (that is mainly refer in the fraction special alkene) equals 1: 1 at least, is preferably between 1: 1 and 20: 1, and above-mentioned mole ratio is 2: 1-6: 1 o'clock then better.
The consumption (by weight) that extracts water in the district is that every part of olefin gasolines charging is comparatively favourable with 0.4-3 part water (preferably 0.7-1.2 part).Under above-mentioned these conditions, catalyzer in time and the degree of inactivation is low.When the water yield was lower than aforementioned proportion, the phenomenon of a large amount of inactivations of catalyzer appearred.
This accompanying drawing is that an explanation is suitable for implementing the schema that complete processing of the present invention various one of may arrangement modes.
This flow chart further shows can be with methyl alcohol with the olefin gasolines etherificate, and only washes with water and can remove excessive methyl alcohol and do not need the distillation reaction device to flow out the operating procedure of this both expensive of thing.
In processing technology shown in the drawings, olefin gasolines imports etherification zone by pipeline (6), etherification zone preferably is made up of two reactors that are connected in series (1) and (2), reactor contains the acid catalysis agent, such as ion exchange resin, for example resemble the sulfonic acid type resin described in the United States Patent (USP) 3037052.
Methyl alcohol imports by pipeline (5), and mixes mutually with gasoline before entering reactor (1). Reactor effluent imports water extraction by pipeline (8) and gets post (3), and post (3) operates under the condition of hydrocarbon and water adverse current. The gasoline of removing the etherificate behind the methyl alcohol is discharged by pipeline (9) and is added in the power fuel pond. Water can enter the extraction post by pipeline (10), and discharges from the bottom of post with its contained methyl alcohol, adds distillation post (4) with separating methanol by pipeline (11) then, and isolated methyl alcohol is by the column top outflow and by pipeline (7) and valve V1Be recycled to the entrance of etherification zone.
In a preferred concrete example, to major general's part methyl alcohol by pipeline (7) and valve V2Be recycled in the reactor (2).
This flow process degree has been illustrated the embodiment example of the present invention, and various different concrete examples can also be arranged in not exceeding scope of the present invention. Particularly etherification zone can be made up of single reactor or two above reactors, and unconverted methyl alcohol is capable of circulation in many reactors wherein.
Preferably methyl alcohol (at least partially) is recycled at least one reactor first reactor. Have at least two modes with series winding to connect in the reactor of etherification zone; Some reactor in the reactor that also can consider to connect connects in a parallel manner.
C with methanol etherification olefin gasolines mixture and cracking4During fraction, it is not gratifying adopting such as the accompanying drawing institute bright processing technology of valve.
In fact can see special alkene (isobutene, iso-amylene, iso-heptene) conversion rate is along with the time reduces gradually, increase gradually along with the time and be used for special butanols (TBA) content that the washing reaction device flows out in the water of thing, therefore correspondingly reduced ether (the receipts rate of MTBE and tertiary amyl methyl ether-TAME).
These impacts can be owing to having dissolved the MTBE that a part generates in the water that is used for extracting methyl alcohol.
In the process of post 4 distillating carbinols, MTBE is flowed out by the top, and owing to azeotropism is taken water out of, these MTBE and water are imported into reactor then and have weakened the operating effect of this complete processing.
Etherificate olefin gasolines and C
4During the fraction mixture, its operation can be undertaken by the method that United States Patent (USP) 4118425 is narrated, and has discarded the water that is used to wash effluent in this method, but has caused the loss of MTBE and methyl alcohol.
On the contrary, author of the present invention sees, under the operate continuously condition, does not contain a large amount of C with methanol etherification
4During the olefin gasolines of hydro carbons (thereby not containing iso-butylene), there is not above-mentioned shortcoming.
This schema is particularly useful for the petroleum naphtha of steam cracker gasoline and catalytic cracking applicable to undersaturated gasoline.
The distillation end point of this catalytic cracking petroleum naphtha is 50-150 ℃.
After treatment, these gasoline contain ether and are substantially free of methyl alcohol.
Following examples are used to illustrate the present invention but do not limit use range of the present invention.
Embodiment 1:(contrast)
With 100 parts of weight distillation end points is 130 ℃, does not contain C
4Hydro carbons and mainly contain C
5, C
6And C
7The catalytic cracking light oil of hydro carbons (isopentene that comprises %8 weight, 6.5% dissident's alkene and 2.5% iso-heptene) and the C of 80 parts of weight (iso-butylene that contains 25% weight)
4Fraction imports reactor (1) by pipeline (6), and the methyl alcohol with 73.5 parts of weight imports reactor inlet simultaneously, is 4 but make the methyl alcohol and the mole ratio of the alkene of etherificate.The methyl alcohol that is imported comprises two portions, the generation ether necessary fresh methanol of a part for importing by pipeline (5), and another part is by pipeline (7) round-robin excessive methanol after post (4) distillation.Charging is that 6 flow velocity imports reactor (1) with volumetric velocity hourly (VVH) under 80 ℃.By the effusive effluent of reactor (1) with VVH 3 flow velocity at 70 ℃ of importing reactors (2) down through heat exchanger (not shown) cooling back.Wash by the effusive effluent of reactor (2) in extraction column (3) with 250 parts of water.Then these are contained methyl alcohol, the washing water of 1-1.5% butyl alcohol-tert (TBA) and 0.6%MTBE distill in post (4).Methyl alcohol and MTBE-H
2O azeotrope (containing 4% water) is discharged by the top and is circulated to reactor (2) by pipeline (7).
Form as shown in table 1 at different time by the effusive effluent of pipeline (8).
Operate after 300 hours, the ether amount that is generated has reduced, and the transformation efficiency of iso-butylene and isopentene has also reduced.
Special conversion of olefines rate is represented with percentage.
Can directly be used as the constituent of gasoline mixture by the effusive product of pipeline (9): except being substantially free of methyl alcohol or TBA, its composition is identical with the effusive effluent of pipeline (8).
Embodiment 2:
With 100 parts of weight have with embodiment 1 in the catalytic cracking petroleum naphtha of identical distillation end point and composition import reactor (1) with 27.8 parts of weight methyl alcohol.
But methyl alcohol is 4 with the mole ratio of the isoolefine total amount of etherificate.
Charging, promptly the flow velocity of gasoline and methyl alcohol is that VVH equals 6.The temperature of reactor inlet remains on 80 ℃.With the cooling of the effluent of reactor (1) make its can be under 70 ℃ be that 3 flow velocity imports reactor (2) with VVH.Use 130 parts of water in post (3), to wash effluent then.The water that will contain methyl alcohol distills in post (4), and the column top obtains pure basically methyl alcohol and is circulated to reactor (1) by pipeline (7).The effluent of pipeline (8) is formed shown in the table II.Can find out that by the table II this composition still remains unchanged after operation 300 hours.In addition, the transformation efficiency of isopentene also is higher than the transformation efficiency of isopentene among the embodiment (1).The output of ether is also higher.Identical by forming of pipeline (9) products therefrom with forming of pipeline (8) effluent, but the former does not contain methyl alcohol.
*Symbol E
tC
7, E
tC
8Represent 7 carbon atoms or 8 carbon atoms respectively.
Claims (9)
1, a raising contains per molecule 5 carbon atom hydro carbons, particularly isopentene, and does not contain the complete processing of the olefinic gasolines of a large amount of 4 carbon atom hydro carbons, it is characterized in that:
A) the olefin gasolines fraction is added etherification zone, react and obtain containing the effluent of tertiary amyl methyl ether at this fraction of etherification zone and methyl alcohol.
B) effluent that a) goes on foot gained is added the extraction district, distinguish water in extraction and extract most of at least unreacted methanol, and reclaim the part of having removed most of methyl alcohol at least and having contained most of tertiary amyl methyl ether.
C) fractionation is by b) the step gained contain aqueous extract, obtaining that methanol content increases and the fraction (α) that water-content has reduced, and methanol content reduces and fraction (β) that water-content has increased.
D) fraction that has increased methanol content to major general's part is recycled to etherification zone, and the fraction that has increased water-content to major general's part is recycled to and extracts the district.
2, complete processing according to claim 1, wherein olefin gasolines is C
5-C
7Fraction.
3, method according to claim 1 and 2, wherein the methyl alcohol in the etherificate effluent carries out counter-current extraction with water.
4, complete processing according to one of claim 1 to 3, wherein etherification zone is made up of two reactors that are connected in series at least.
5, complete processing according to claim 4, wherein round-robin methyl alcohol is recycled to the inlet of a reactor except that first reactor at least in part.
6, complete processing according to one of claim 1-5, but be 1: 1 to 20: 1 wherein in the mole ratio of the methyl alcohol of etherification zone inlet and the alkene of etherificate.
7, complete processing according to one of claim 1-6, but be 2: 1 to 6: 1 wherein in the mole ratio of the methyl alcohol of etherification zone inlet and the alkene of etherificate.
8, complete processing according to one of claim 1-7, wherein the used water yield (by weight) is 0.4-3 part water/every part of olefin gasolines charging in (b) step.
9, complete processing according to one of claim 1-7, wherein the used water yield (by weight) of (b) step is 0.4-1.2 part water/every part of olefin gasolines charging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105107 CN1006716B (en) | 1985-07-04 | 1985-07-04 | Process for upgrading olefinic gasolines by etherification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105107 CN1006716B (en) | 1985-07-04 | 1985-07-04 | Process for upgrading olefinic gasolines by etherification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105107A true CN85105107A (en) | 1986-12-31 |
| CN1006716B CN1006716B (en) | 1990-02-07 |
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ID=4794263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105107 Expired CN1006716B (en) | 1985-07-04 | 1985-07-04 | Process for upgrading olefinic gasolines by etherification |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085648C (en) * | 1997-05-07 | 2002-05-29 | 中国石化齐鲁石油化工公司 | Light hydrocarbon etherifying technology |
-
1985
- 1985-07-04 CN CN 85105107 patent/CN1006716B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085648C (en) * | 1997-05-07 | 2002-05-29 | 中国石化齐鲁石油化工公司 | Light hydrocarbon etherifying technology |
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| Publication number | Publication date |
|---|---|
| CN1006716B (en) | 1990-02-07 |
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