CN1191330C - Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline - Google Patents
Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline Download PDFInfo
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- CN1191330C CN1191330C CNB001107305A CN00110730A CN1191330C CN 1191330 C CN1191330 C CN 1191330C CN B001107305 A CNB001107305 A CN B001107305A CN 00110730 A CN00110730 A CN 00110730A CN 1191330 C CN1191330 C CN 1191330C
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Abstract
The present invention relates to a method for preparing gasoline without benzene by the reaction of olefin and gasoline containing benzene, which comprises the following steps: in the presence of a powdered catalyst, the gasoline containing benzene and the olefin carry out hydrocarbylation reaction in a slurry bed reactor; tail gas in the effluent after reaction is exhausted; the obtained liquid product is the desired gasoline without benzene. The method has the advantages of simple technological process, less investment, low power consumption, etc.
Description
The present invention relates to a kind of novel process that benzoline and olefin alkylation reaction are produced unbenzoled petrol that contains, be particularly suitable for containing the process that benzoline and rare ethene and/or rare propylene alkylation prepare unbenzoled petrol.
In existing gasoline production process; in order to improve the octane value of gasoline; added a certain amount of benzene; enhancing gradually along with human environmental consciousness; benzene in the gasoline causes people's attention day by day to the harm of environment and human body; west major industrial country has begun to limit the content of benzene in the gasoline now; requirement is less than 1%; China has also begun the legistration work of this respect; therefore be necessary very much the existing benzoline that contains is prepared low benzene or unbenzoled petrol by certain method, to reach the protection environment requirement.
Catalytic cracked dry gas is the tail gas of refinery's by-product, wherein contains ethene 10～30%, and propylene 1～8% if use it for from containing the process that benzoline prepares unbenzoled petrol, can be saved the pure ethylene raw material, opens up new way for catalytic cracked dry gas effectively utilizes.
Since the 1980s, developed from containing the method that benzoline prepares unbenzoled petrol.For the conversion that contains benzene in the benzoline, a kind of process is by hydrogenation benzene to be converted into hexanaphthene, and another kind of process is by with olefin alkylation benzene being converted into alkylbenzene.
US4997543, US5149894, US5210348, US5491270 etc. have reported the method for preparing unbenzoled petrol by alkene and the alkylation process that contains benzoline in succession, and catalyzer is conventional alkylation catalyst, and reactor adopts fixed bed or tank reactor.In these processes, the highest per pass conversion of benzene has only 80%, can not only reach the purpose of producing unbenzoled petrol by a step alkylated reaction.Just because of this, other is arranged to improve the patent appearance that the benzene transformation efficiency is a purpose again.
US5210348 has reported the combination process of benzene alkylation and benzene hydrogenation.Its process is in a fixed-bed catalytic distillation reactor, contains benzoline and contains lower concentration C
2-C
4Olefin gas is under the catalysis of ZSM-5 equimolecular sieve catalyst, at 350～450 °F, 150～300psig, under the reaction conditions of LHSV=1～3, alkylated reaction taking place, makes 30～50% benzene be converted into alkylbenzene, rely on the distillment of reaction zone, benzene separates with alkylate, and the benzene in the petroleum naphtha of top under catalyst action hydrogenation/isomerization reaction takes place, and generates C
5～C
7Alkane, thus whole conversions of benzene finished.
US5336820 has reported and has a kind ofly made benzene be converted into the process of alkylbenzene by alkylation fully.Adopt fluidized-bed reactor, catalyzer is mesoporous molecular sieve ZSM-5, and C is adopted in its alkylation earlier
3 =～C
5 =Alkene is alkylating agent, and then uses C
2 =Alkene is alkylating agent, contains benzoline in regular turn by two alkylation stages, and the content of benzene is less than 1% in the final gasoline.
CN1097187A has reported a kind of with AlCl
3--CH
2Cl
2Being catalyzer, is alkylating agent with FCC gas, and with the process that tank reactor is produced ethylbenzene, its byproduct is a unbenzoled petrol.
The object of the present invention is to provide a kind of method that benzoline and olefine reaction are produced unbenzoled petrol that contains, the one way clearance height of its benzene, technical process are simple, reduced investment, energy consumption are low.
The invention provides a kind of method that benzoline and olefine reaction are produced unbenzoled petrol that contains, it is characterized in that: in the presence of powder catalyst, raw material contains benzoline and alkene, in paste state bed reactor, carry out alkylation reaction, tail gas emptying in the alkylation reaction effluent, product liquid is unbenzoled petrol, and the solid powdery catalyzer is retained in the reactor always; The condition of alkylation reaction is granularity 100 orders of catalyzer, 80～290 ℃ of temperature of reaction, and reaction pressure 0.3～10.0MPa, the mol ratio of benzene is 3～1 in alkene and the gasoline, the weight space velocity of benzene is 0.05～0.5 o'clock in the gasoline
-1, stirring velocity is 100～2000 rev/mins.
Alkylation reaction can adopt a plurality of placed in-line paste state bed reactors in the inventive method, reactor is n, n=1～10, the gas that contains alkene divides several sections addings, contain benzoline and add from first reactor, the tail gas in first reactor effluent is discharged through condensation reflux device, and product liquid is then as the charging of second reactor, carry out alkylation reaction with alkene again at second reactor, the rest may be inferred for all the other each reactors.
The raw materials used alkene of the present invention is pure or rare alkene, does not wherein contain free-water, H in rare alkene
2S content＜3000mg/M
3, CO
2≤ 4% volume; Preferably adopt C
2 =And/or C
3 =
Specifically the present invention can use the ethene that contains lower concentration and/or the plant catalytic cracking of propylene or the dry gas of catalytic pyrolysis or thermo-cracking to be alkylating agent, and this dry gas does not need refining especially, enters slurry attitude bed alkylation reaction device bottom with containing benzoline.Slurry attitude bed alkylation reaction device can be provided with n, n=1～10, the tail gas that each reactor upper space is discharged, through a condensation reflux device, the gas phase gasoline component that tail gas is carried becomes liquid and turns back to the alkylation reaction device, liquid in the alkylation reaction device is sent into second alkylation reaction device bottom through a strainer and pipeline, mix with new dry gas and to carry out hydrocarbonylation, the rest may be inferred for the situation of other each alkylation reaction device, the final reaction product is sent into the absorption extraction device, because the centrifugation of strainer is stayed in the alkylation reaction device solid powder th-1 catalyst all the time, the liquid level of alkylation reaction device is determined by the installation site of strainer and liquid discharge tube line.The speed of rotation of stirring arm should smash the bubble of the unstripped gas sent into as far as possible, and with reactor wall on traverse baffle coupling is set, thereby reduced the resistance to mass transfer that alkene is dissolved in the diffusional resistance and the olefine reaction of liquid phase effectively.The direct emptying of residue rare gas element that a last reactor is discharged, can not produce diluting effect to the raw material olefin of next reactor, relatively improved the concentration of olefin of each reactor, alkylation reaction speed has been accelerated in above measure, helps improving the processing power of unit catalyzer.Below with ethene in the catalytic cracked dry gas and/or propylene and contain the process that benzoline prepares unbenzoled petrol and be illustrated, but not thereby limiting the invention.
(1) reaction raw materials: alkylation reaction is a reaction raw materials to contain benzoline, rare ethene and/or propylene.Material dilute ethylene and propylene are the dry gas that contains low-concentration ethane and/or propylene from refinery's device, need not special purified, only otherwise contain free-water, H
2S content＜3000mg/M
3, CO
2≤ 4% volume.
(2) catalyzer: the catalyzer that alkylation reaction uses can be general sial and silicon phosphorus aluminium zeolite, preferred y-type zeolite, the β zeolite, Md zeolite and MCM-22 zeolite, adopt conventional treatment process to carry out upgrading, distribute with strength of acid and the acid of regulating zeolite, for example use mineral acid (example hydrochloric acid, nitric acid), organic acid (as acetic acid) was handled 0.5～10 hour to the boiling condition in room temperature, perhaps use high-temperature roasting (450～800 ℃) 2～10 hours, perhaps use water vapour (10～100% dividing potential drop) to handle 1～8 hour down etc. at 300～650 ℃, the Y of the upgrading that obtains, β, Md and MCM-22 zeolite add porous material Al
2O
3.xH
2O or clay molding bonded promptly can be used as the hydrocarbonylation catalyzer.
(3) process operation parameter
The process operation parameter of reaction is: the granularity of catalyzer＞100 orders, 80～290 ℃ of temperature of reaction, reaction pressure 0.3～10.0MPa, C
2 =And C
3 =With weight space velocity 0.05～0.5 of the mol ratio 3～1 of benzene, benzene o'clock
-1, 100～2000 rev/mins of the stirring velocitys of slurry attitude bed agitator.
To be further specified the present invention by example below, but not thereby limiting the invention.
Accompanying drawing 1 is technical process of the present invention.
Example 1～3
Accompanying drawing 1 is seen in technical process, and alkylation reaction device (1) is a plurality of placed in-line paste state bed reactors, is two reactors of A and B shown in the figure.Contain after the benzoline heating, add the A reactor from the bottom by pipeline (6), and from the rare ethene and the propylene feedstocks of catalytic cracked dry gas, without special purified, directly enter the A reactor bottom through pipeline (5), under the effect of solid powder th-1 catalyst, generate ethylbenzene, diethylbenzene, isopropyl benzene and diisopropyl benzene etc. with the benzene reaction.In the A reactor head, the remaining rare gas element in reaction back enters condensation reflux device (2) through pipeline (11), the gasoline component of gas-entrained is cooled to liquid turns back to the A reactor, and tail gas enters through pipeline (7) and separates and absorption tower (3).Product liquid enters the B reactor bottom from the pipeline (12) of correct position through strainer is housed on A reactor top, mix with the cold dry gas that enters the B reactor, carry out alkylation reaction under the solid powder th-1 catalyst effect in the B reactor, the rest may be inferred for the situation of all the other each reactors, and the effluent of last alkylation reaction enters through pipeline (8) and separates and absorption tower (3).
Gas-liquid separation is carried out with the product liquid of alkylation reaction device A and B tail gas discharged and B reactor in separation and absorption tower (3), and the gas quilt of telling is through pipeline (9) emptying, and liquid flows out through pipeline (10) and is unbenzoled petrol at the bottom of the tower.
When adopting an independent slurry attitude bed alkylation reaction device, the internal diameter of reactor is 70mm, the liquid height 182mm of controlling reactor the inside.The FCC dry gas directly enters reactor bottom without refining, contains benzoline and enter reactor bottom simultaneously after preheating.FCC dry gas (volume %) composed as follows: CH
430.5, C
2H
424.0, C
2H
615.2, C
3H
65.6, C
3H
82.5, H
29.4, N
27.3, CO1.1, CO
24.0, O
20.4, H
2S3000mg/M
3, H
2O1100ppm, the content that contains benzene in the benzoline is 10%.Alkylation reaction condition and the results are shown in Table 1.
Example 4～8
Adopt two slurry attitude bed alkylation reaction device serial operations, the FCC dry gas is divided into two stocks and does not advance first reactor and second reactor bottom, and the unbenzoled petrol of two reactor needs adds from first reactor bottom.The FCC dry gas of the size of alkylation reaction device and use is identical with example 1.Other operation steps also with example 1～3 in identical, the results are shown in Table 1.
Table 1
| The hydrocarbonylation of slurry attitude bed | Number of reactors | An independent alkylation reaction device | Two alkylation reaction device series connection | |||||||
| Example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Catalyzer loading amount (g) | First reactor | 20 | 50 | 90 | 20 | 20 | 30 | 50 | 50 | |
| Second reactor | -- | -- | -- | 20 | 20 | 30 | 50 | 50 | ||
| Reaction pressure (MPa) | 1.00 | 2.00 | 1.10 | 0.95 | 1.50 | 1.50 | 1.10 | 3.00 | ||
| Temperature of reaction (℃) | 175 | 210 | 174 | 171 | 200 | 200 | 172 | 245 | ||
| Total alkene/benzene (molecular ratio) | 2.0 | 1.0 | 2.0 | 1.0 | 2.5 | 1.5 | 2.0 | 3 | ||
| Total benzene air speed (WHSV) | 0.11 | 0.11 | 0.11 | 0.10 | 0.16 | 0.13 | 0.12 | 0.25 | ||
| Catalyst type | β | MCM-22 | Y | β | β | MCM-22 | Y | Y | ||
| Stirring velocity (rev/min) | 700 | 1000 | 500 | 500 | 700 | 1000 | 500 | 1200 | ||
| The transformation efficiency of benzene (%) | 96.3 | 97.2 | 96.9 | 97.0 | 98.1 | 97.9 | 97.8 | 98.5 | ||
Claims (4)
1 one kinds contain the method that benzoline and olefine reaction are produced unbenzoled petrol, it is characterized in that: in the presence of powder catalyst, raw material contains benzoline and alkene, in paste state bed reactor, carry out alkylation reaction, tail gas emptying in the alkylation reaction effluent, product liquid is unbenzoled petrol, and the solid powdery catalyzer is retained in the reactor always; The condition of alkylation reaction is granularity＞100 orders of catalyzer, 80～290 ℃ of temperature of reaction, and reaction pressure 0.3～10.0MPa, the mol ratio of benzene is 3～1 in alkene and the gasoline, the weight space velocity of benzene is 0.05～0.5 o'clock in the gasoline
-1, stirring velocity is 100～2000 rev/mins.
2 contain the method that benzoline and olefine reaction are produced unbenzoled petrol according to claim 1 is described, it is characterized in that: described alkylation reaction adopts one or more placed in-line paste state bed reactors, reactor is n, n=1～10, the gas that contains alkene divides several sections addings, containing benzoline adds from first reactor, tail gas in first reactor effluent is discharged through condensation reflux device, product liquid is then as the charging of second reactor, carry out alkylation reaction with alkene again at second reactor, the rest may be inferred for all the other each reactors.
3 according to the described alkene of claim 1 with contain the method that benzoline is produced unbenzoled petrol, it is characterized in that: do not contain free-water, H in the alkene in the raw materials used alkene
2S content＜3000mg/M
3, CO
2≤ 4% volume.
4 according to described alkene of claim 3 and the method that contains benzoline system unbenzoled petrol, and it is characterized in that: raw materials used alkene adopts C
2 =And/or C
3 =
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001107305A CN1191330C (en) | 2000-07-26 | 2000-07-26 | Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline |
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|---|---|---|---|
| CNB001107305A CN1191330C (en) | 2000-07-26 | 2000-07-26 | Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline |
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|---|---|
| CN1335358A CN1335358A (en) | 2002-02-13 |
| CN1191330C true CN1191330C (en) | 2005-03-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440302B (en) * | 2008-12-22 | 2013-02-13 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
| US8395006B2 (en) * | 2009-03-13 | 2013-03-12 | Exxonmobil Research And Engineering Company | Process for making high octane gasoline with reduced benzene content by benzene alkylation at high benzene conversion |
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