CN1198431A - Light hydrocarbon etherifying technology - Google Patents
Light hydrocarbon etherifying technology Download PDFInfo
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- CN1198431A CN1198431A CN97105845A CN97105845A CN1198431A CN 1198431 A CN1198431 A CN 1198431A CN 97105845 A CN97105845 A CN 97105845A CN 97105845 A CN97105845 A CN 97105845A CN 1198431 A CN1198431 A CN 1198431A
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Abstract
The present invention relates to a technological process for etherification of tertiary olefine being in the hydrocarbon raw material of C5 and its upwards. Said invention utilizes the characteristics of light hydrocarbon which can be mixed with alcohol below C4, and formed into aceotrope to make the residual methyl alcohol after reaction and C5 form azeotrope, and make it circulate between the reactor and azeotrope, and make it circulate between the reactor and azeotropic distillation tower or catalytic distillation tower so as to save the methyl alcohol recovering system.
Description
The present invention relates to a kind of technology that carbon five and above hydro carbons etherificate thereof is prepared contain in the gasoline oxygen to add component, specifically, the invention relates to and make C
5～C
8Tertiary olefin and the corresponding ether of methyl alcohol prepared in reaction.
For the explosion-proof performance of improving lead-free fuel oil, the concentration that reduces objectionable constituent in the discharging tail gas, countries such as the U.S., West Europe stipulate that to the content of oxygenatedchemicals in the gasoline production technology that contains oxygen ethers interpolation component has obtained developing rapidly.The ether compound that adopts has methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE), tert amyl methyl ether(TAME) (TAME), tertiary amyl ethyl ether (TAEE) and methyl-tert hexyl ether (THME) etc. at present.Owing to contain the active higher low-carbon alkene (C of atmosphere in the gasoline
5～C
8), its etherificate not only can be reduced the objectionable constituent of discharging in the tail gas, and can improve the content of oxygenatedchemicals in the gasoline, thereby the etherificate technology of carbon five and above tertiary olefin thereof comes into one's own day by day in the gasoline.
Tertiary olefin is thermopositive reaction with the reaction that alcohol generates ether, and its peak rate of conversion is determined by the thermal equilibrium of reaction system.In order to improve the transformation efficiency of reaction, people have developed two anti-two tower process (promptly carrying out two secondary responses, twice separation processes) and catalytic distillation technology, but its complex technical process, required equipment is more, and react residue methyl alcohol and want first water extraction, again water-methanol solution is distilled to reclaim and to recycle methyl alcohol.A kind of new technology of being announced in the International Application No. WO 93/19032 has then overcome above-mentioned shortcoming, it is characterized in that utilizing a spot of carbon four and methyl alcohol to form azeotrope, to carry unreacted methanol, thereby saved methanol recovery system, but the mol ratio of methyl alcohol and tertiary olefin has influenced the transformation efficiency of etherification reaction less than 1 (0.7～0.9) in this technology; And the C in the raw material
4With C
5Need to finish separation, thereby increased the height of tower body at the rectifying section of distillation tower; Simultaneously, because C
5The content of iso-pentane is the highest in the above hydro carbons, and boiling point is minimum again, and it is dense to make side line extract the position iso-pentane out, and tertiary olefin content is lower, reach high transformation efficiency, will increase internal circulating load, makes the side line reactor volume huge, and energy consumption also increases relatively.In addition, in WO 93/19032 disclosed technology, methyl alcohol and carbon four form azeotrope, leave the main reaction tower from cat head, but also will add methyl alcohol in addition in the side line reactor, have increased the internal circulating load of methyl alcohol.
Because C from FCC
5Above component does not contain C substantially
4, as if the C that can utilize wherein
5Also form the character of azeotrope, its azeotrope is circulated between main reaction tower and side line reactor, just can in raw material, add artificially and regulate C with methyl alcohol
4Amount, can cancel methanol recovery system so on the one hand, solve C
4Carry the problem that agent brings, can reach higher transformation efficiency again on the other hand.
In the present invention, what be concerned about is not the pure ether product of preparation, but produce the etherificate product that can add composition as gasoline, or directly gasoline is carried out etherificate and handle, make the active high alkene of atmosphere tertiary olefin and the methyl alcohol formation ethers that reacts especially wherein, the quantity discharged of harmful component in the time of can reducing gasoline combustion like this, the while can be improved the explosion-proof performance of gasoline again.
Thereby purpose of the present invention is utilized C exactly
5With the character of methyl alcohol formation azeotrope, develop a kind of direct use C
5And above hydrocarbon makes the technology of raw material, makes C wherein
5～C
8Tertiary olefin and methyl alcohol generation etherification reaction.
According to the present invention, methyl alcohol (or other low-carbon alcohol) and C
5And the raw material (C of above hydro carbons
5 +) enter main reactor after, under the effect of catalyzer, C
5 +In tertiary olefin and methyl alcohol generation addition reaction, generate corresponding ethers; Post reaction mixture comprises ether and the unreacted hydrocarbon and the methyl alcohol of generation entering azeotropic distillation column, and through heat and mass transport process repeatedly, ether and heavier hydro carbons are shifted to the tower still in tower, and overhead materials is mainly C
5Azeotrope and unreacted light hydrocarbon component with methyl alcohol; Overhead materials is after condensation, and a part loops back azeotropic distillation column as phegma, and a part is recycled in the main reactor, utilizes the methyl alcohol in the azeotrope, improves the alfin ratio of material in the main reactor, and rest part then enters in the auxiliary reactor and reacts; The tower still thing of auxiliary reactor comprises ether and most of unreacted C of generation
5And above hydro carbons, turn back to the suitable position of azeotropic distillation column, still unreacted methanol and portion C
5Form azeotrope, turn back in the main reactor by the cat head of paying reactor.
Above-mentioned C
5And the raw material of the above hydro carbons light ends fractionation that can be produced for catalytic cracking, steam cracking, delayed coking etc.
In the present invention, adjustment enters into inventory of paying reactor and the internal circulating load that turns back to main reactor by azeotropic distillation column, can adjust the methanol content in the etherification product and the transformation efficiency of active tertiary olefin, make the requirement that touches the mark of methanol content in the product.
Major and minor reactor of the present invention can be fixed-bed reactor, and flow direction of material can be from top to bottom, also can be from bottom to top.Main reactor also can adopt bubble point reactor and expanded bed reactor.Used catalyzer is an acidic solid catalyst, as macroporous ion exchange resin and molecular sieve etc.Catalyzer in the main reactor can load on small amount of precious metals such as palladium, platinum, nickel etc., it had simultaneously select hydrogenation to take off diolefin, the olefin isomerization of non-activity turned to the function of active olefin and etherificate.
The pressure of reactor can be 0.2～2.0MPa, and temperature can be chosen between 40～200 ℃, and the volume space velocity of reaction mass is 0.5～10h
-1
Azeotropic distillation column is traditional distillation tower in the present invention, can be tray columns such as float valve, sieve plate, also can be the packing tower of various fillers.From using, azeotropic distillation column can be divided into three districts (seeing accompanying drawing), and each theoretical plate number that needs is 5～20, and wherein: I is a rectifying section, and main effect is to prevent that a large amount of ethers and heavy hydrocarbons from moving into distillate to cat head; II is the dual function district, under the effect of column plate or filler, both can make the unreacted tertiary olefin that comes from main reactor move to the top of tower, can make the ether that comes from auxiliary reactor etc. move to the tower still again; III is a stripping section, and main effect is to prevent that methyl alcohol from moving into tower still effluent to the tower still.Experiment and result calculated show that all the theoretical plate number of rectifying section generally should not be lower than 5, otherwise can contain more tert amyl methyl ether(TAME) in the overhead product, thereby influence the transformation efficiency of tertiary olefin in the auxiliary reactor; The theoretical plate number of stripping section generally should not be lower than 5, otherwise guarantee that with regard to being difficult to the methanol concentration in the tower bottoms is lower than the desired value of defined (as 1000ppm), but stage number is also too much unsuitable, and as surpassing 20, the carbon five with methyl alcohol formation azeotrope just is not difficult for draining from the tower still.
The tower top temperature of azeotropic distillation column is 40～100 ℃, and pressure is 0.3～1.5MPa, and reflux ratio is 0.2～20, is respectively 0.1～10 times of inlet amount to the liquid measure that distillates of major and minor reactor.
Active tertiary olefin described in the present invention comprises 2-methyl-1-butene alkene, 2-methyl-2-butene, 2-Methyl-1-pentene, 2-methyl-2-amylene, suitable-3-methyl-2-amylene, anti--3-methyl-2-amylene, 2-ethyl-1-butylene, 2, the individual C that similar molecular structure is arranged surplus the 3-dimethyl-1-butylene, 2,3-dimethyl-2-butylene, 1-methyl cyclopentene etc. 60
5～C
8Tertiary olefin; Described alcohols comprises low-carbon alcohol such as methyl alcohol, ethanol, Virahol.
C
5 +Raw material can carry out purifying treatment before entering reactive system, comprise processes such as water washing cleaning and selection hydrogenation, and purpose is to remove the deleterious material of used solid acid catalyst.
Water washing cleaning can adopt typical continuous countercurrent extraction tower, raw material hydrocarbon from bottom to top, water is from top to bottom, two-phase is carried out mass exchange on column plate or filler, metal ion in the hydrocarbon, basic nitrogen compound etc. are taken off, made its concentration, to prevent that itself and etherificate are with the H on the resin catalyst less than 1ppm
+Ion-exchange takes place, or makes it to come off with the sulfonic acid group reaction.
Selecting hydrogenation then is in order to take off the diolefin in the hydrocarbon, because very easily polymerization on catalyst for etherification of diolefin, the blocking catalyst duct makes reactive material can not arrive active centre in the duct, causes catalyst activity reduction.In addition, the formed colloid of diolefin polymerization also influences quality of gasoline.Select the used catalyzer of hydrogenation to be generally the precious metal that is carried on the carrier, as Pd-Al
2O
3, Ni-Al
2O
3Deng, used reactor is trickle-bed reactor or bubbling bed reactor.With Pd-Al
2O
3During for catalyzer, its processing condition are: pressure 0.5～2.0MPa, and temperature is 50～150 ℃, air speed is 0.5～5.0h
-1, the mol ratio of hydrogen and diolefin is 1.5～5.0 (mol/mol).
The initial stage of driving, the material of the high alfin ratio of pumping or methyl alcohol in system earlier, make the methyl alcohol in azeotropic distillation column rectifying section, condenser and the return tank be accumulated to certain value, generally can detect methyl alcohol in the azeotropic distillation column tower bottoms and methanol concentration is lower than certain value such as 1000ppm exceeds.Drive normal after, the methanol feeding amount is reduced to normal value, that is makes methyl alcohol (concentration is lower than the desired value of permission) that methyl alcohol that methanol feeding amount and reaction consumes are fallen and product take away quite.In main reactor, but the C of methyl alcohol and etherificate
5, C
6The mol ratio of tertiary olefin can reach 0.7～1.0; In auxiliary reactor, the mol ratio of methyl alcohol and uncle's amylene can reach 1.05～1.3, need not to pay reactor again and adds methyl alcohol.
In the present invention, azeotropic distillation column and auxiliary reactor can replace with a catalytic distillation tower, and flow process as shown in Figure 2.C after material benzenemethanol and the purification
5 +At first carry out etherificate in fixed-bed reactor, make tertiary olefin and methyl alcohol addition generate corresponding ethers, post reaction mixture enters catalytic distillation tower.Catalytic distillation tower can be divided into rectifying section I, catalytic distillation section II and stripping section III.In catalytic distillation tower, C
6The component that reaches high boiling points such as above hydro carbons, ethers is shifted to the tower still under the effect of column plate or filler; C
5And then move up with the azeotrope of methyl alcohol, enter the catalytic distillation section, when carrying out the etherificate reversible reaction, also carrying out separating of reactant and product, thereby reaction is carried out towards the direction that helps resultant, improved the transformation efficiency of reaction; Light constituent is proceeded to separate after rising to rectifying section I, makes unreacted C
5The higher 2-methyl-2-butene of mid-boiling point forms with liquid phase again and turns back to the catalytic distillation section, will separate from the ether that the catalytic distillation section is carried secretly up simultaneously, is recycled in the fixed-bed reactor to prevent it.The key that reaches the catalytic distillation effect be how catalyst loading in catalytic distillation tower.For diameter commonly used is 0.3～1.2 millimeter ion-exchange resin catalyst, can adopt our patent structure, sees Chinese patent 88109705.5 (authorization notification number CN 1022382) and U.S. Pat 5,523,061 for details.
The overhead product of catalytic distillation tower enters return tank after condenser condenses, a part is operated needed phegma as catalytic distillation tower, and part is introduced this tower near the position of bottom, makes most of C
5Discharge a small amount of C from the tower still
5Form azeotrope with methyl alcohol, moving up enters the catalytic distillation section, and methyl alcohol is further transformed.
In this scheme of the present invention, the pattern of main reactor, flow direction of material and operational condition are identical with last scheme; The tower top temperature of catalytic distillation tower is 40～90 ℃, and pressure is 0.3～1.5MPa, and reflux ratio is 0.2～20, and the amount that phlegma is circulated to main reactor is 0～10 times of inlet amount, and the amount that is incorporated into catalytic distillation tower stripping section bottom is 1～5 times of inlet amount.
The present invention directly utilizes C
5 +C in the raw material
5Form azeotrope to carry unreacted methanol with methyl alcohol, saved methanol recovery system; Simultaneously avoided in raw material, adding artificially C again
4Carry the problem that methyl alcohol brings.Processing unit is simple relatively, can reach higher tertiary olefin transformation efficiency again.
Below in conjunction with accompanying drawing, further specify the present invention by embodiment.
Fig. 1 is the process flow sheet (flow direction of material from top to bottom) when adopting two reactors and a distillation tower scheme;
Fig. 2 is the process flow sheet when adopting a reactor and a catalytic distillation tower scheme.
Embodiment 1
Adopt technical process shown in Figure 1, experimental raw is the catalytically cracked gasoline mid-boiling point less than 60 ℃ cut.(Φ 80 * 1000mm) and auxiliary reactor 4 (are equipped with the macroporous ion exchange resin of 4 liters and 3.2 liters respectively among the Φ 80 * 1000mm) at main reactor 1; The specification of azeotropic distillation column 2 is Φ 50 * 2500mm, is divided into rectifying section I, dual function district II and stripping section III, and it highly is respectively 800,1000 and 700mm, interior dress Φ 6 * 6 Double-level Reticulated rings.The temperature in of main reactor 1 is 60 ℃, and pressure is 0.6MPa, and raw material inlet amount (not containing recycle stream) is 6 liters/hour; The tower top temperature of azeotropic distillation column is 70 ℃, and pressure is 0.35MPa, and quantity of reflux is 3 liters/hour, and the internal circulating load to main reactor is 3 liters/hour, and the mass flow to auxiliary reactor is 5.5 liters/hour; The temperature in of auxiliary reactor is 65 ℃.Methanol content in the products obtained therefrom is 0.07%, and the transformation efficiency of active uncle's amylene is 89.6%, C
6The transformation efficiency of tertiary olefin is 41.0%.Embodiment 2
Adopt reaction unit, flow process and the operational condition identical with embodiment 1, raw material then adopts the C in the catalytically cracked gasoline
5Cut.The transformation efficiency that records active uncle's amylene is 85.32%, and the methanol content in the product is 0.04%.
Claims (10)
1, a kind of C that makes
5And above hydro carbons etherificate prepares oil fuel and contains the technology that oxygen adds component, may further comprise the steps:
(1) C
5And above hydro carbons and methyl alcohol enters in the main reactor, and under the effect of solid acid catalyst, tertiary olefin wherein and methyl alcohol generation addition are anti-main, generate corresponding ether;
(2) post reaction mixture enters azeotropic distillation column, and an overhead product part is as phegma, and a part is circulated to main reactor, and all the other then enter auxiliary reactor;
(3) ether and the most of unreacted C that generates in the auxiliary reactor
5And above hydro carbons turns back to azeotropic distillation column, unreacted methanol and portion C from the tower still of auxiliary reactor
5Form azeotrope, be back in the main reactor by the cat head of auxiliary reactor;
(4) effluent that is obtained by the tower still of azeotropic distillation column can be used as the interpolation component of oil fuel, comprises ether and unreacted hydro carbons that reaction generates;
This technology is characterised in that:
Reaction remaining methyl alcohol in back and C
5Form azeotrope, the reaction system internal recycle of forming at main reactor, azeotropic distillation column and pair reactor utilizes, need not be again to the Methanol Recovery utilization.
2. the described technology of claim 1 is characterized in that the solid acid catalyst that reacts used is macroporous ion exchange resin or molecular sieve.
3. the described technology of claim 2 is characterized in that load has a spot of noble metal component such as platinum, palladium, nickel above the used solid acid catalyst.
4. the described technology of claim 1 is characterized in that the temperature of reaction of reactor is controlled at 40～200 ℃, and pressure-controlling is at 0.2～2.0MPa.
5. the described technology of claim 1 is characterized in that used azeotropic distillation column is tray column or packing tower, and tower top temperature is controlled at 40～150 ℃, and pressure-controlling is at 0.2～2.0MPa, and control of reflux ratio is 0.1～10.
6. the described technology of claim 1, the overhead product that it is characterized in that azeotropic distillation column to auxiliary reactor and the main reactor amount and the ratio control of inlet amount be 0.1～1.0 and 0～5.
7. the described technology of claim 1 is characterized in that used C
5And the raw material of above hydro carbons is the light ends fractionation that catalytic cracking, steam cracking, delayed coking etc. are produced.
8. the described technology of claim 1 is characterized in that C
5And hydrotreatment is washed or selected to above hydrocarbon raw material before entering reactor.
9. the described technology of claim 1 is characterized in that azeotropic distillation column and auxiliary reactor replace with a catalytic distillation tower.
10. the described technology of claim 9 is characterized in that the tower top temperature of catalytic distillation tower is controlled at 40～90 ℃, and pressure-controlling is at 0.3～1.5MPa, and control of reflux ratio is 0.2～20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105845A CN1085648C (en) | 1997-05-07 | 1997-05-07 | Light hydrocarbon etherifying technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105845A CN1085648C (en) | 1997-05-07 | 1997-05-07 | Light hydrocarbon etherifying technology |
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| Publication Number | Publication Date |
|---|---|
| CN1198431A true CN1198431A (en) | 1998-11-11 |
| CN1085648C CN1085648C (en) | 2002-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97105845A Expired - Fee Related CN1085648C (en) | 1997-05-07 | 1997-05-07 | Light hydrocarbon etherifying technology |
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|---|---|
| CN (1) | CN1085648C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN102433159A (en) * | 2011-09-22 | 2012-05-02 | 凯瑞化工股份有限公司 | Catalytic gasoline light fraction etherification process |
| CN102492463A (en) * | 2011-12-09 | 2012-06-13 | 宁夏宝塔石化集团应用技术研究院（有限公司） | Hydrocarbon washing refining method |
| CN102492466A (en) * | 2011-12-09 | 2012-06-13 | 宁夏宝塔石化集团应用技术研究院（有限公司） | Process and device for producing catalytic gasoline by etherifying |
| CN107686745A (en) * | 2017-09-26 | 2018-02-13 | 丹东明珠特种树脂有限公司 | A kind of Etherification of Light FCC Gasoline system and its Etherification of Light FCC Gasoline process |
| CN113058283A (en) * | 2021-03-01 | 2021-07-02 | 中国石油化工股份有限公司 | Methanol recovery system and process of MTBE (methyl tert-butyl ether) device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1006716B (en) * | 1985-07-04 | 1990-02-07 | 法国石油公司 | Process for upgrading olefinic gasolines by etherification |
| CN1018524B (en) * | 1989-07-25 | 1992-10-07 | 中国石油化工总公司 | Catalytic distillation colum |
| CN1044805C (en) * | 1994-08-30 | 1999-08-25 | 中国石油化工总公司 | Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol |
-
1997
- 1997-05-07 CN CN97105845A patent/CN1085648C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN102408316B (en) * | 2010-09-21 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN102433159A (en) * | 2011-09-22 | 2012-05-02 | 凯瑞化工股份有限公司 | Catalytic gasoline light fraction etherification process |
| CN102433159B (en) * | 2011-09-22 | 2014-04-02 | 凯瑞化工股份有限公司 | Catalytic gasoline light fraction etherification process |
| CN102492463A (en) * | 2011-12-09 | 2012-06-13 | 宁夏宝塔石化集团应用技术研究院（有限公司） | Hydrocarbon washing refining method |
| CN102492466A (en) * | 2011-12-09 | 2012-06-13 | 宁夏宝塔石化集团应用技术研究院（有限公司） | Process and device for producing catalytic gasoline by etherifying |
| CN107686745A (en) * | 2017-09-26 | 2018-02-13 | 丹东明珠特种树脂有限公司 | A kind of Etherification of Light FCC Gasoline system and its Etherification of Light FCC Gasoline process |
| CN107686745B (en) * | 2017-09-26 | 2020-06-12 | 丹东明珠特种树脂有限公司 | Light gasoline etherification system and light gasoline etherification process method thereof |
| CN113058283A (en) * | 2021-03-01 | 2021-07-02 | 中国石油化工股份有限公司 | Methanol recovery system and process of MTBE (methyl tert-butyl ether) device |
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|---|---|
| CN1085648C (en) | 2002-05-29 |
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