CN106554807A - The high-octane rating etherified benzine production technology of low sulfur, low olefin - Google Patents
The high-octane rating etherified benzine production technology of low sulfur, low olefin Download PDFInfo
- Publication number
- CN106554807A CN106554807A CN201510634159.3A CN201510634159A CN106554807A CN 106554807 A CN106554807 A CN 106554807A CN 201510634159 A CN201510634159 A CN 201510634159A CN 106554807 A CN106554807 A CN 106554807A
- Authority
- CN
- China
- Prior art keywords
- low
- octane rating
- sulfur
- light
- production technology
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to technical field of petrochemical industry, and in particular to a kind of high-octane rating etherified benzine production technology of low sulfur, low olefin.Alcohol will be added in light gasoline fraction A to make alkene therein be converted into high-octane rating oxidized compound by reaction；The feed separation for obtaining is at least light, weighs two kinds of fraction Bs and C by fractionation, adopt the method for solvent extraction heavy distillat C to be processed to remove sulphur compound therein, obtain heavy distillat D after desulfurization；Fraction B, D are mixed, the high-octane rating etherified benzine of low sulfur, low olefin is obtained.Light petrol of the present invention is while reducing content of olefin in gasoline, improving octane number by etherification reaction, it is divided into two strands of cuts of weight, heavy distillat is removed into sulphur compound therein using the method for solvent extraction only, the raw material of solvent extraction is few, desulfurization energy consumption, low cost.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of high-octane rating etherified benzine production work of low sulfur, low olefin
Skill.
Background technology
With going from bad to worse for environment, restriction of the countries in the world to harmful substances such as the sulphur in gasoline, alkene is more and more harsh, I
The state IV motor petrol standard that state performs at present required that sulfur content is less than 28% less than 50ppm, olefin(e) centent, from 2018
The state V standards for performing in China are required into that sulfur content is less than 24% less than 10ppm, olefin(e) centent.
Content of sulfur in gasoline is greatly lowered mainly using two kinds of techniques of S Zorb desulfurization and hydrodesulfurization, above-mentioned technique can all bring vapour
The loss of oily octane number.Etherification of Light FCC Gasoline technology is, using the be etherified alkene in light gasoline fraction, to refer mainly to carbon five, six alkene of carbon
Hydrocarbon, generates tert amyl methyl ether(TAME) (TAME), methyl- tert hexyl ether (THXME) etc. with high-octane with methyl alcohol reaction
Ether mixture, the technology can both reduce content of olefin in gasoline, can improve octane number, effectively solving gasoline desulfurization again
The loss of octane number for causing.
Light petrol raw material for etherificate is that full distillation gasoline cuts gasoline of the boiling point isolated below 60-110 DEG C through cut
Cut, typically by the lightweight Mercaptan removal in gasoline during cut cutting, so typically without low in light gasoline fraction
Boiling mercaptans.
The method of the production low sulfur, low olefin gasoline described in United States Patent (USP) US7431827 is by gasoline point in a catalytic distillation tower
From for light petrol, two strands of cuts of heavy petrol, while to Ta Neitong hydrogen, there are three kinds of reactions altogether in tower built with catalyst, in tower,
Low boiling mercaptan and diene hydrocarbon reaction form higher sulfide (" thioetherification reaction "), higher sulfide from bottom of towe with
Heavy petrol flows out, so as to realize that low boiling mercaptan is separated with light petrol, while it is monoolefine and list that diolefin hydrogenate occurs
The isomerization reaction of alkene.Then the monoolefine in light fraction is etherified to generate ether with alcohol, or is hydrogenated to generate alcohol with water.
Heavy distillat carries out removal of sulphur by hydrodesulfurization or chemisorbed.Finally merge two kinds of cuts and obtain low sulfur, low olefin gasoline.
Chinese patent 200710064669 provides a kind of Etherification of Light FCC Gasoline technique and the gasoline method for remanufacturing containing the technique, by FCC
Alkadienes and mercaptan sulfur in the chosen property hydrogenation and removing gasoline of gasoline, after hydrogenation by full distillation gasoline cut into gently, weigh two components,
Bis- sections of light petrol Jing is etherified into ether compound, the hydrogenated desulfurating and reducing olefinic hydrocarbon of heavy petrol, the heavy petrol after hydrogenation can Jing extracting aromatic hydrocarbons,
Heavy petrol after extracting aromatic hydrocarbons can both make the raw material of steam heat cracking ethylene preparation, also can reconcile with etherified benzine and produce for clean gasoline
Product.
Chinese patent 201410781964 discloses a kind of method for Deep Desulfurization of FCC Gasoline, including：First paragraph is anti-
Should be thioetherification reaction, after reaction, gasoline is cut into weight two parts by rectifying column, second segment reaction is that heavy constituent selectively adds
Hydrogen desulfurization and isomerization, hydrodesulfurization of the 3rd section of reaction for secondary mercaptan after selective hydrodesulfurization process, the 4th section is anti-
Etherification of Light FCC Gasoline is should be, last light, biharmonic obtains meeting the super low-sulfur oil product of state's V gasoline quality standards.
What above-mentioned technology was adopted is all by the technique of the removal of sulfur compounds in light petrol, this work before Etherification of Light FCC Gasoline technique
Skill has that the removal of sulfur compounds in light petrol is halfway.Make mercaptan and alkadienes that thioetherification reaction occur only by hydrogenation
Can the sulphur compound that exists with mercaptan form of removing, be suitable to the light petrol boiling range upper limit being etherified at 60-110 DEG C or so, key component
For C5, C6 hydrocarbon, containing a small amount of C7 hydrocarbon, and numerous studies are also existed in being proved the hydro carbons of more than C6 and are deposited with forms such as thiophene
Sulphur compound, the sulphur compound in light petrol is at most dropped to by 10-15ppm by this sulfur removal technology.Light petrol to be reached,
After heavy petrol mixing, sulfur content is required less than the state V standards of 10ppm, must improve the depth of heavy petrol hydrodesulfurization, and loss is more
Many octane numbers.Some techniques in order to the sulphur compound in light petrol is taken off below 10ppm, using reduce light petrol boiling range on
The method of limit, the light gasoline fraction for cutting out are mainly C5 hydrocarbon, because sulphur compound therein is mainly mercaptan, by early stage
Pretreatment can be removed.But such light gasoline fraction is reduced as raw material of etherification, the amount that can be etherified alkene, certainly will cause ether
The gasoline olefin amount that chemical industry skill is reduced is reduced, and the octane number of increase is reduced.
Chinese patent 201310416658 discloses a kind of for sulfur-bearing in oil refining enterprise and chemical industry removing catalytically cracked gasoline
The catalytically cracked gasoline sulfur method of compound and device.Light FCC gasoline or catalytic cracking full distillate gasoline are added by the method
Enter extraction distillation column, Jing multitple extractions distillation desulfurization, for producing country IV or the motor petrol of state's V standards.As the technique is
By light FCC gasoline or catalytic cracking full distillate gasoline all through extractive distillation desulfurization, thus the energy consumption of desulfurization, cost compared with
It is high.
The content of the invention
It is an object of the invention to provide a kind of high-octane rating etherified benzine production technology of low sulfur, low olefin, light petrol is anti-in etherificate
It is divided into two strands of cuts of weight during olefin(e) centent should be reduced, heavy distillat is removed into sulfuration therein using the method for solvent extraction
Compound, overcomes the halfway problem of removal of sulfur compounds and light petrol desulfurization energy consumption, high cost in light petrol in prior art
Problem.
The high-octane rating etherified benzine production technology of low sulfur, low olefin of the present invention, step are as follows：
(1) alcohol will be added in light gasoline fraction A to make alkene therein be converted into high-octane rating oxidized compound by reaction；
(2) feed separation that step (1) is obtained is at least light, weighs two kinds of fraction Bs and C, using solvent extraction by fractionation
Method process heavy distillat C to remove sulphur compound therein, obtain heavy distillat D after desulfurization；
(3) fraction B, D are mixed, obtains the high-octane rating etherified benzine of low sulfur, low olefin.
Light gasoline fraction A boiling points described in step (1) are less than 110 DEG C, and preferred light gasoline fraction A boiling points are less than 80 DEG C.
Light gasoline fraction A described in step (1) removes low boiling mercaptan therein.
Solvent described in step (2) is sulfolane, dimethylformamide, N-N-formyl morpholine N, triethanolamine or N-methyl
One or more in pyrrolidones.Solvent extraction effect of the present invention is good, it is easy to reclaim.
The method of the solvent extraction described in step (2) is comprised the following steps：
(A) heavy distillat C is entered from extraction tower middle and lower part, and solvent entered from the top of extraction tower, and heavy distillat C Jing extraction desulfurizations are from taking out
Stripper ejects tower, obtains the heavy distillat D after desulfurization, and the solvent for having extracted sulfide goes out tower from bottom of towe, obtains material E；
(B) material E enters solvent recovery tower, isolates sulfur-rich component F from tower top, isolates solvent from bottom of towe, will be described molten
Agent returns described extracting tower top, recycles.
Solvent described in step (A) is controlled in 0.5-3.0 with the charge ratio of heavy distillat C, is preferably controlled in 1.0-3.0.
At 50-90 DEG C, extracting column bottom temperature is 60-110 DEG C to extracting tower top temperature control described in step (A), extracts tower top
Pressure is 0.1-0.6MPa.
Technique of the present invention is particularly suited for catalytic cracking or catalytic cracking gasoline, light gasoline fraction and a certain amount of alcohol such as first
The methyltertiarvbutyl ether reactor of filling acidic etherification catalysts is entered after alcohol mixing, the alkene in light gasoline fraction is converted into into higher octane
Feed separation after etherificate, while reducing olefin(e) centent, is at least light, weighs two kinds of cuts by fractionation by the ether compound of value,
Light fraction is preferably cut of the boiling point below 40-50 DEG C, and key component is C5 hydrocarbon, and double distilled is divided into containing ethers oxidized compound
And the mixture of more than C6 hydro carbons.In order to improve conversion ratio, save energy consumption, preferably above-mentioned etherification reaction is separated with light and heavy fractions
Carry out in a catalytic distillation tower, the alkene more preferably in light gasoline fraction is first reacted in methyltertiarvbutyl ether reactor, is reached
Catalytic distillation tower is entered back into after certain conversion ratio, is continued reaction and is separated simultaneously.Methyltertiarvbutyl ether reactor and catalytic distillation tower can
With any one form using prior art, acidic etherification catalysts can be any one general catalyst for etherification,
Preferred cationic exchanger resin, molecular sieve.
Described etherification reaction is in pressure 0.1-2MPa, temperature 40-120 DEG C, air speed 1-10h-1Under the conditions of carry out.
Containing the remaining alcohol of reaction in the described light fraction after etherification reaction, extractant can be adopted alcohol from described light
Separate in cut, then alcohol and extractant are separated by distillation, the alcohol for obtaining can return the circulation of etherification reaction part and make
With.
Typically by the lightweight Mercaptan removal in full gasoline fraction during cut cutting, so in light gasoline fraction typically not
Mercaptan containing low boiling.Numerous studies prove that the sulphur compound in C5 gasoline fractions is essentially all mercaptan, more than C6 gasoline fractions
In also exist with the forms such as thiophene exist sulphur compound.So etherificate after light petrol in isolated light fraction
Not sulfur compound.If containing low boiling mercaptan compound in light gasoline fraction, the present invention can remove light before step (1)
Low boiling mercaptan in gasoline fraction, the method that caustic extraction oxidation can be adopted.Light petrol first passes through a caustic extraction tower,
Low boiling mercaptan in light gasoline fraction is extracted by alkali lye, then converts mercaptans to disulphide by air catalytic oxidation
Removing regeneration, the alkali lye after regeneration are recycled.Low boiling mercaptan compound is not contained through the light gasoline fraction of caustic extraction,
The light fraction isolated after etherification reaction is substantially free of any sulfide, and sulfide is existed only in heavy distillat.
Through solvent extraction sulfur method of the present invention, sulphur compound is reduced to 10ppm even 5ppm for described heavy distillat
Below.
Described sulfur-rich component F sends to heavy petrol hydrodesulfurization unit or diesel hydrotreating unit is processed and reclaims organic matter therein.
The present invention compared with prior art, has the advantages that：
(1) the low sulfur, low olefin etherified benzine production technology that the present invention is provided, the removal of sulfur compounds in light gasoline fraction are thorough,
Not only it is stripped of the sulphur compound of mercaptan form, and is stripped of the sulphur compound of other forms of thiophene, thioether etc, desulfurization
Sulphur compound in etherified benzine cut meets requirement of the state V gasoline standards to sulfur content less than 10ppm even 5ppm afterwards,
Can be separately as gasoline blend component.
(2) the low sulfur, low olefin etherified benzine production technology that the present invention is provided, light petrol are reducing gasoline alkene by etherification reaction
While hydrocarbon content, raising octane number, it is divided into two strands of cuts of weight, only heavy distillat is removed using the method for solvent extraction
Sulphur compound therein, the raw material of solvent extraction are few, desulfurization energy consumption, low cost.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
In figure：A, light gasoline fraction；B, light fraction B；C, heavy distillat C；D, heavy distillat D；E, material E；F, richness
Sulphur component F；G, alcohol；H, etherified benzine；I, methyltertiarvbutyl ether reactor；J, catalytic distillation tower；K, extraction tower；L, solvent
Recovery tower.
Specific embodiment
With reference to embodiments the present invention is described further.
Embodiment 1-4
Light gasoline fraction A is mixed with methyl alcohol, into the methyltertiarvbutyl ether reactor of filling cation exchange resin catalyst, light petrol is evaporated
Alkene in point is converted into high-octane ether compound, while reducing olefin(e) centent, reacted mixed material is entered back into urges
Change destilling tower, continue reaction and separated simultaneously.The feed separation after etherificate is light, weighs two kinds of cuts by separating, gently evaporated
B is divided to be C5 hydrocarbon, heavy distillat C is the mixture containing ethers oxidized compound and more than C6 hydro carbons.Etherification reaction is in pressure
0.1-2MPa, temperature 40-120 DEG C, air speed 1-10h-1Under the conditions of carry out.
Heavy distillat C is entered from extraction tower middle and lower part, solvent is entered from the top of extraction tower, and heavy distillat C Jing extraction desulfurizations are from extracting
Tower top goes out tower, obtains the heavy distillat D of desulfurization, and the solvent for having extracted sulfide goes out tower from bottom of towe, obtains material E；Material E enters
Entering solvent recovery tower, sulfur-rich component F being isolated from tower top, isolate solvent from bottom of towe, the solvent is returned into described extracting
Top of tower, recycles.At 50-90 DEG C, extraction tower bottom temperature control extracts tower top at 60-110 DEG C to extracting tower top temperature control
Stress control is in 0.1-0.6MPa.
Fraction B, D are mixed, the high-octane rating etherified benzine cut of low sulfur, low olefin is obtained, sulfur content is down to 10ppm very
To below 5ppm, can be separately as gasoline blend component.
Sulfur-rich component F that solvent recovery tower top is isolated is sent to diesel hydrotreating unit and processes recovery organic matter therein.
The process conditions and Contrast on effect of embodiment 1-4 are shown in Table 1.
The process conditions and Contrast on effect of 1 embodiment 1-4 of table
Claims (7)
1. the high-octane rating etherified benzine production technology of a kind of low sulfur, low olefin, it is characterised in that step is as follows：
(1) alcohol will be added in light gasoline fraction A to make alkene therein be converted into high-octane rating oxidized compound by reaction；
(2) feed separation that step (1) is obtained is at least light, weighs two kinds of fraction Bs and C, using solvent extraction by fractionation
Method process heavy distillat C to remove sulphur compound therein, obtain heavy distillat D after desulfurization；
(3) fraction B, D are mixed, obtains the high-octane rating etherified benzine of low sulfur, low olefin.
2. the high-octane rating etherified benzine production technology of low sulfur, low olefin according to claim 1, it is characterised in that step
(1) the light gasoline fraction A boiling points described in are less than 110 DEG C.
3. the high-octane rating etherified benzine production technology of low sulfur, low olefin according to claim 1, it is characterised in that step
(1) the light gasoline fraction A described in removes low boiling mercaptan therein.
4. the high-octane rating etherified benzine production technology of low sulfur, low olefin according to claim 1, it is characterised in that step
(2) solvent described in is sulfolane, dimethylformamide, N-N-formyl morpholine N, triethanolamine or N-methyl pyrrolidone
In one or more.
5. the high-octane rating etherified benzine production technology according to the arbitrary described low sulfur, low olefin of claim 1-4, its feature exist
The method of the solvent extraction described in step (2) is comprised the following steps：
(A) heavy distillat C is entered from extraction tower middle and lower part, and solvent entered from the top of extraction tower, and heavy distillat C Jing extraction desulfurizations are from taking out
Stripper ejects tower, obtains the heavy distillat D after desulfurization, and the solvent for having extracted sulfide goes out tower from bottom of towe, obtains material E；
(B) material E enters solvent recovery tower, isolates sulfur-rich component F from tower top, isolates solvent from bottom of towe, will be described molten
Agent returns described extracting tower top, recycles.
6. the high-octane rating etherified benzine production technology of low sulfur, low olefin according to claim 5, it is characterised in that step
(A) solvent described in is controlled in 0.5-3.0 with the charge ratio of heavy distillat C.
7. the high-octane rating etherified benzine production technology of low sulfur, low olefin according to claim 5, it is characterised in that step
(A) at 50-90 DEG C, extracting column bottom temperature is 60-110 DEG C to the extracting tower top temperature control described in, and extracting tower top pressure is
0.1-0.6MPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510634159.3A CN106554807B (en) | 2015-09-30 | 2015-09-30 | The high-octane rating etherified benzine production technology of low sulfur, low olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510634159.3A CN106554807B (en) | 2015-09-30 | 2015-09-30 | The high-octane rating etherified benzine production technology of low sulfur, low olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554807A true CN106554807A (en) | 2017-04-05 |
| CN106554807B CN106554807B (en) | 2018-09-21 |
Family
ID=58415955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510634159.3A Active CN106554807B (en) | 2015-09-30 | 2015-09-30 | The high-octane rating etherified benzine production technology of low sulfur, low olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106554807B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766057A (en) * | 2004-10-27 | 2006-05-03 | 催化蒸馏技术公司 | Process for the production of low sulfur, low olefin gasoline |
| CN102381945A (en) * | 2011-09-05 | 2012-03-21 | 西南石油大学 | Method and device for removing organic sulfur in methyl tertiary butyl ether (MTBE) |
-
2015
- 2015-09-30 CN CN201510634159.3A patent/CN106554807B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766057A (en) * | 2004-10-27 | 2006-05-03 | 催化蒸馏技术公司 | Process for the production of low sulfur, low olefin gasoline |
| CN102381945A (en) * | 2011-09-05 | 2012-03-21 | 西南石油大学 | Method and device for removing organic sulfur in methyl tertiary butyl ether (MTBE) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554807B (en) | 2018-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103214332B (en) | Method for producing light aromatic hydrocarbons and high-quality oil products from catalytically cracked diesel | |
| CN104479738B (en) | A kind of Deep Desulfurization of FCC Gasoline combination process | |
| CN102212394B (en) | Fluid catalytic cracking (FCC) gasoline modification method comprising light gasoline etherification process | |
| CN101649221B (en) | Method for producing reforming feedstock by light and medium gasoline distillates | |
| CN105296000A (en) | Coupling method of catalytic cracking gasoline desulfurization | |
| CN103361118B (en) | Method for recovering aromatic hydrocarbons from gasoline containing olefin and sulfide | |
| CN103555359B (en) | Deep desulfurization method for catalytically cracked gasoline | |
| CN102337153B (en) | Hydrotreatment method of gasoline distillate oil | |
| CN102399585B (en) | Method for producing sweet gasoline | |
| CN104726132A (en) | Process For The Hydrodesulphurization Of Hydrocarbon Cuts | |
| CN106554813B (en) | The high-knock rating gasoline production technology of low sulfur, low olefin | |
| WO2010083642A1 (en) | System and process for producing high quality gasoline by recombination and subsequent hydrogenation of catalytic hydrocarbons | |
| CN103059955B (en) | Method for producing clean gasoline from catalytic cracking gasoline | |
| CN106554807B (en) | The high-octane rating etherified benzine production technology of low sulfur, low olefin | |
| CN106883872B (en) | Deep gasoline desulfurization device adopting and method | |
| CN107163982A (en) | A kind of method for extracting extracting rectifying reduction regeneration oil recovery sulfur content | |
| CN108329946B (en) | Method for separating gasoline fraction and gasoline desulfurization method | |
| CN108424786B (en) | Separation method of gasoline fraction and gasoline desulfurization method | |
| CN105907422B (en) | A kind of production technology of low-sulphur oil | |
| CN102604672B (en) | Method for producing low-sulfur gasoline | |
| CN105950214B (en) | A kind of production method of low-sulphur oil | |
| CN113122326B (en) | Deep desulfurization method for full-fraction catalytic cracking gasoline | |
| CN102533325B (en) | Method for producing low-sulfur gasoline | |
| CN103087770A (en) | Clean gasoline production method through selective hydrogenation and desulfurization of catalytic gasoline | |
| WO2009067885A1 (en) | A system and process for producing high quality gasoline by catalytic hydrocarbon recombination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |