CN102757815B - A kind of method reducing benzene content in reformed oil - Google Patents
A kind of method reducing benzene content in reformed oil Download PDFInfo
- Publication number
- CN102757815B CN102757815B CN201110109863.9A CN201110109863A CN102757815B CN 102757815 B CN102757815 B CN 102757815B CN 201110109863 A CN201110109863 A CN 201110109863A CN 102757815 B CN102757815 B CN 102757815B
- Authority
- CN
- China
- Prior art keywords
- benzene
- cut
- rich
- reaction
- reformed oil
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Reduce a method for benzene content in reformed oil, comprise the rich benzene cut of reformed oil and C
2~ C
4alkene contact under the existence of alkylation catalyst and carry out alkylated reaction, contacted in the presence of a transalkylation catalyst with the rich benzene cut of reformed oil by polyalkylbenzene cut in alkylation reaction product and carry out transalkylation reaction, the rich benzene cut of described reformed oil is the cut of in reformed oil 60 ~ 95 DEG C.This method significantly can reduce the benzene content in reformed oil, and without loss of octane number, without yield of gasoline loss, product is done and is no more than gasoline boiling range, directly can enter gasoline pool, also without the need to subsequent separation process.
Description
Technical field
The present invention is a kind of method reducing benzene content in oil product, specifically, is a kind of method reducing benzene content in reformed oil.
Background technology
Along with improving constantly and automobile exhaust pollution day by day serious of environmental consciousness, environmental regulation is also increasingly strict to the restriction of motor vehicle exhaust.Because benzene is carcinogenic substance, bad meeting of burning makes benzene content in exhaust emission increase, and harm public health, so countries in the world are comparatively strict to the requirement of Determination of Benzene In Gasoline, has the trend reduced further to the limits value of its content.At present, state IV motor spirit standard is not more than 1.0 volume % to being restricted to of benzene content.Along with the more harsh motor spirit benzene content of California, USA implementation is not more than the standard of 0.62 volume %, China also likely implements more harsh benzene content in gasoline standard.At western developed country, the benzene content of reformed gasoline is 0.2 ~ 8 volume %, is 75 ~ 80% to the contribution of benzene content in whole gasoline pool; Although the scale that China reforms is relatively little, and is restructured as master with aromatic hydrocarbons type, reformate benzene content exceeds standard and is still the bottleneck that reformate enters gasoline pool.On the one hand along with the continuous expansion of China's reforming process scale, the ratio that reformate enters gasoline pool increases gradually, and reformate benzene content excessive problem will inevitably be more and more serious; On the other hand, Chemical market periodically also requires that exploitation reduces the technology of reformate benzene content, and when purified petroleum benzin price is lower, the benzene huge and stable stop bracket gasoline market of demand that can come into the market is sold as commercial gasoline.
The method reducing reformate benzene content has three kinds: 1. select suitable reformer feed and operation scheme, 2. remove benzene and the benzene precursor of reformer feed, 3. remove the benzene in reformed oil.
Select suitable reformer feed and resurfacing operation scheme can reduce the benzene content of reformed oil, but be often subject to raw material sources, the impact of the factors such as refinery's unified planning, adjusting range is limited, can not meet the requirement that reformate benzene content reduces.
The benzene and the benzene precursor that remove reformer feed are the methods that the selectable Low investment in current refinery reduces reformate benzene content.Before raw material enters reformer, by the C in raw material
6the precursor of component benzene and benzene is removed by the method for distillation, to realize the object reducing product reformate oil benzene content.But can not avoid the generation of benzene in reforming process, thus reformate benzene content reduces limited extent, and the C of the low octane rating height benzene content cut out
6cut still needs further process, can enter gasoline pool.
The benzene removed in reformed oil has two large class methods.Be a method for physical sepn, as absorption, distillation, another kind is chemical transformation.Absorption method utilizes the benzene in specific sorbent material selective adsorption gasoline, and its shortcoming is loss yield of gasoline, loses high-octane number component simultaneously, benzene and other aromatic hydrocarbons, alkene competitive adsorption seriously, and adsorbent finite capacity.Reformed oil distillation cuts out rich benzene cut, and low benzene cut admission oil sump is the method for the main reduction reformate benzene content of current China.Although the method can conveniently reduce reformate benzene content, due to the limitation of distillating method, low benzene cut benzene content reduces limited extent.At present, debenzolized oil benzene content controls at 2.0 below volume %, can meet the requirement of the rear benzene content in gasoline of mediation at 1.0 below volume %.
The benzene content that chemical transformation removes in reformed oil is high because of its de-benzene handiness, falls benzene amplitude and is subject to extensive concern greatly.Mainly contain hydrotreated lube base oil and take off benzene and alkylation takes off benzene two kinds of methods.
USP7175754 discloses a kind of method of producing low benzene content gasoline, by saturated for the benzene hydrogenation in gasoline be hexanaphthene, although this method significantly can reduce the benzene content in gasoline, but hydrogen consumption is high, have loss of octane number and complex process, and the low octane rating oil product after de-benzene still needs process further to enter gasoline pool.
Alkylation de-benzolized technology utilizes the benzene generation alkylated reaction in external light olefin resource and reformed oil to generate the object that alkylbenzene realizes reducing reformate benzene content.Alkylation takes off benzene to be had higher benzene transformation efficiency, the increase of oil product octane value because of it, is subject to extensive concern without features such as hydrogen consumptions.US4827069 discloses a kind of method making light olefin and catalytic reforming generate its quality of oil reaction lifting in turbulent fluidized bed, by C
4following light olefin and reformed oil react, and conversion of olefines is become C
5 +hydrocarbon, simultaneously by C
6~ C
8aromatic conversion become C
7~ C
11aromatic hydrocarbons.
USP7476774 discloses a kind of liquid phase alkylating aromatic hydrocarbon method, uses MWW type zeolite, if MCM-22 is catalyzer, makes refinery's light olefin and reformed oil carry out alkylated reaction, to reduce the benzene content of reformed oil.
Although benzene technology falls in alkylation plurality of advantages, because it carries out under the condition of lower benzene/alkene molecular ratio, inevitably generate polyalkylbenzene, thus make product do rising to exceed gasoline boiling range.
US2010/0044273A
1disclose a kind of method being reduced reformed oil benzene content by transalkylation reaction, full cut reformed oil is divided at least three kinds of cuts, a kind of lighting end containing benzene, a kind of containing C
7~ C
9middle runnings, the one of monoalkyl aromatic hydrocarbon contain C
10 +the cut of heavy arene, contacts lighting end with heavy arene, makes benzene wherein and C
10 +in many alkylaromatic hydrocarbons generation transalkylation reaction formed monoalkyl aromatic hydrocarbon.
Summary of the invention
The object of this invention is to provide a kind of method reducing benzene content in reformed oil, the rich benzene cut in reformed oil is carried out alkylation and transalkylation two-step reaction by this method, significantly can reduce the benzene content in reformed oil.
The method of benzene content in reduction reformed oil provided by the invention, comprises the rich benzene cut of reformed oil and C
2~ C
4alkene contact under the existence of alkylation catalyst and carry out alkylated reaction, contacted in the presence of a transalkylation catalyst with the rich benzene cut of reformed oil by polyalkylbenzene cut in alkylation reaction product and carry out transalkylation reaction, the rich benzene cut of described reformed oil is that in reformed oil, boiling range is the cut of 60 ~ 95 DEG C.
The present invention is by the rich benzene cut in reformed oil and alkylation reactions, the alkylate generated carries out rectifying cutting again, polyalkylbenzene cut is carried out transalkylation reaction with rich benzene cut again, effectively can utilize the heavy constituent in alkylate, it is made to be converted into monoalkylated benzenes, thus the overall benzene content reduced in reformed oil.
Embodiment
Rich benzene cut in reformed oil and light olefin are carried out alkylated reaction by the present invention, more much higher for alkylation reaction product mid-boiling point alkylbenzene is separated, transalkylation reaction is carried out again with rich benzene cut, thus the benzene content reduced in gasoline, solve alkylate simultaneously and do the problem exceeding gasoline boiling range.The inventive method significantly can reduce the benzene content in reformed oil, and without loss of octane number, without yield of gasoline loss, product is done and is no more than gasoline boiling range, directly can enter gasoline pool, also without the need to subsequent separation process.
The rich benzene cut of reformed oil cuts out and carries out alkylated reaction by the present invention from reformed oil.The boiling range of described rich benzene cut preferably 75 ~ 90 DEG C.In the rich benzene cut of described reformed oil, benzene content is 20 ~ 50 volume %, preferably 30 ~ 50 volume %.
The alkylating agent rich benzene cut being carried out alkylated reaction is C
2~ C
4alkene, described C
2~ C
4alkene optimal ethylene, propylene or butylene.
The temperature preferably 100 ~ 300 DEG C of alkylated reaction, more preferably 110 ~ 280 DEG C, pressure is 0.1 ~ 6.0MPa preferably.Benzene in alkylation process in rich benzene cut and C
2~ C
4the molecular ratio of alkene is 1 ~ 8, preferably 3 ~ 6.Alkene is 0.5 ~ 50h by the mass space velocity of alkylation catalyst bed layer
-1, preferred 1.0 ~ 10h
-1.
In the alkylate of rich benzene cut, the boiling point of polyalkylbenzene is higher, exceed the boiling range scope of gasoline, therefore the polyalkylbenzene Component seperation in alkylate is out become polyalkylbenzene cut by the present invention, described polyalkylbenzene component refers to have and exceedes the substituent alkylbenzene of two or more, as dialkyl benzene, trialkyl benzene.Be the alkylated reaction of alkylating agent for ethene, polyalkylbenzene is mainly diethylbenzene, triethyl-benzene; Be the alkylated reaction of alkylating agent for propylene, polyalkylbenzene is mainly diisopropylbenzene(DIPB), tri-isopropyl benzene.The initial boiling point of polyalkylbenzene cut is greater than 160 DEG C, preferably 160 ~ 180 DEG C, and wherein the content of polyalkylbenzene is 20 ~ 60 quality %, preferably 30 ~ 50 quality %.
The temperature of polyalkylbenzene cut and rich benzene cut being carried out transalkylation reaction is 120 ~ 350 DEG C, preferably 150 ~ 300 DEG C, and pressure is 0.1 ~ 6.0MPa, preferably 1.0 ~ 4.0MPa.In transalkylation reaction, the molecular ratio of the benzene in rich benzene cut and the polyalkylbenzene in polyalkylbenzene cut is 0.6 ~ 7.5, preferably 0.6 ~ 5.0.
In the present invention, described alkylation catalyst and transalkylation catalyst are selected from acidic zeolite or heteropolyacid, one or more in preferred MFI, FAU, MOR, MWW, MTW, TON, MTT, MEL, FER, EON, BEA, AFI, MAZ, IWW and NES structural zeolite of described acidic zeolite.
The preferred β of described alkylation catalyst, ZSM-5, MCM-22, mordenite, ITQ-2, MCM-36, MCM-49, MCM-56 zeolite or heteropolyacid, the silica/alumina molar ratio of ZSM-5 zeolite used is 30 ~ 80.Preferred Y, β, USY, MCM-22, MCM-36, MCM-49 or MCM-56 zeolite of described transalkylation catalyst.The silica/alumina molar ratio of MCM-22 zeolite is 20 ~ 50.
Described zeolite molecular sieve both can directly use, and used, the preferred silicon-dioxide of binding agent or aluminum oxide after also can mixing with binding agent.
One or more in the preferred phospho-wolframic acid of described heteropolyacid, silicotungstic acid, phospho-molybdic acid, silicomolybdic acid, germanotungstic acid, germanium molybdic acid and their salt.For giving full play to the catalytic activity of heteropolyacid and being convenient to reclaim catalyzer, usually use after loaded by heteropoly acid.Conventional carrier has the sieve and silica-sesquioxide of silica gel, gac, carbide resin, zeolite, aluminum oxide, oxidation of interim metal, various natural or synthetic.The carrying method of heteropolyacid is a lot, and as pickling process, absorption method, ion exchange method, sol-gel method, coprecipitation method etc., conventional is pickling process and absorption method.Heteropolyacid of the present invention can with commercial goods or by the preparation of traditional acidifying extracted with diethyl ether method.The preparation method of heteropolyacid normal salt, heteropolyacid acid salt can adopt prior art to prepare: by the carbonate of the stoichiometric heteropolyacid aqueous solution and metal or hydroxide aqueous solution mixing, fully stir for some time under normal temperature, normal pressure after, by water evaporate to dryness, obtain heteropolyacid normal salt or acid salt.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
3.0g alkylation catalyst and 3.0g transalkylation catalyst is loaded respectively in two fixed bed high-pressure micro-devices, described alkylation catalyst is that (Jian Chang company produces industrial ethylbenzene alkylation catalyst, the trade mark is AEB-2), containing the H beta-molecular sieve of 60 quality %, the aluminum oxide of 40 quality %.Described transalkylation catalyst is industrial transalkylation catalyst (Jian Chang company produces, and the trade mark is AEB-1), and containing the HY molecular sieve of 70 quality % and the aluminum oxide of 30 quality, wherein the silica/alumina molar ratio of HY molecular sieve is 5.0.
(1) alkylated reaction is carried out
Be the reformed oil rectifying of 6.8 volume % by benzene content, cut out the rich benzene cut 715g that boiling range is 65 ~ 95 DEG C, its benzene content is 20.08 volume %.Rich for 700g benzene cut and propylene are passed into the micro-reactor loading alkylation catalyst, makes benzene/propylene molecules ratio be 3: 1, at 180 DEG C, 3.0MPa, propylene mass space velocity 1.0h
-1condition under there is the alkylated reaction of propylene and benzene, after having reacted, alkylation reaction product and propylene are carried out second time alkylated reaction by above-mentioned reaction conditions, then second time reaction gained alkylate and propylene are carried out third time alkylated reaction by described condition.Through above-mentioned three alkylideneization reactions, in rich benzene cut, benzene transformation efficiency is 60 quality %, and doing of alkylation reaction product is 205 DEG C, wherein C
9 +aromaticity content is 5.6 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts out many cumene fraction 25g that boiling range is 160 ~ 220 DEG C, in described many cumene fraction, diisopropylbenzene content is 23.1 quality %, triisopropyl benzene content is 2.5 quality %.Be that the rich benzene cut 15g of 65 ~ 95 DEG C mixes with many cumene fraction 25g the micro-reactor passing into and load transalkylation catalyst by boiling range, 220 DEG C, carry out transalkylation reaction under the condition of 3.0MPa, the molecular ratio controlling benzene and many isopropyl benzenes (diisopropyl benzene and triisopropylbenzene sum) during reaction is 1: 1, rich benzene cut mass space velocity 7.0h
-1.Polyisopropylbenzene transformation efficiency is 98 quality %, and it is 176 DEG C that product is done.
The rich benzene cut of above-mentioned 65 ~ 95 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 6.05 volume %, remain after cut mixes with reformate cutting, benzene content is 1.20 volume %.
Comparative example 1
By the method for example 1 (1) step, alkylation process is carried out to reformed oil, but do not carry out (2) step transalkylation reaction.
Be the reformed oil rectifying of 6.8 volume % by benzene content, cut out the rich benzene cut 715g that boiling range is 65 ~ 95 DEG C, its benzene content is 20.08 volume %.Rich benzene cut and propylene are carried out alkylation process by the method for example 1 (1) step, and through three alkylideneization reactions, in rich benzene cut, benzene transformation efficiency is 60 quality %, and doing of alkylation reaction product is 205 DEG C, wherein C
9 +aromaticity content is 5.6 quality %.
The rich benzene cut of above-mentioned 65 ~ 95 DEG C is after alkylation process, and alkylate and reformed oil cutting are remained after cut mixes, the benzene content of mix products is 1.32 volume %, and doing is 205 DEG C.
Example 2
This example alkylation catalyst used is ZSM-5 molecular sieve, and its silica/alumina molar ratio is 50, and Chang Ling catalyst plant is produced; Transalkylation catalyst is USY molecular sieve, and its silica/alumina molar ratio is 5.2, and Chang Ling catalyst plant is produced.
(1) alkylated reaction is carried out
Cut rich benzene cut 730g by the method for example 1, rich for 700g benzene cut and ethene are carried out alkylated reaction, and alkylation catalyst is ZSM-5 molecular sieve.Controlling benzene/ethylene molecule ratio during reaction is 2: 1, and alkylated reaction temperature is 200 DEG C, pressure is 4.0MPa, the mass space velocity of ethene is 1.0h
-1.By example 1 method through three alkylideneization reaction after, benzene transformation efficiency is 40.3 quality %, and doing of the alkylate obtained is 210 DEG C, wherein C
9 +aromaticity content is 5.8 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts out many ethylbenzene cut 30g that boiling range is 160 ~ 220 DEG C, in described many ethylbenzene cut, diethylbenzene content is 30.2 quality %, triethyl-benzene content is 6.3 quality %.Be that the rich benzene cut 30g of 65 ~ 95 DEG C passes into the micro-reactor loading transalkylation catalyst and carries out alkylated reaction by many ethylbenzene cut and boiling range, the molecular ratio controlling benzene and many ethylbenzene is 1: 1,200 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 8.2h under the condition of 3.0MPa
-1, diethylbenzene transformation efficiency 95 quality %, triethyl-benzene transformation efficiency 100 quality %, it is 172 DEG C that product is done.
The rich benzene cut of above-mentioned 65 ~ 95 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 10.26 volume %, remain after cut mixes with reformate cutting, benzene content is 1.72 volume %.
Example 3
Alkylation and transalkylation catalyst are MCM-22 molecular sieve, silica/alumina molar ratio be 30 [according to document A.Corma, C.Corell, J.P é rez-Pariente, Zeolites 15 (1995) 2-in-1 one-tenth)].
(1) alkylated reaction is carried out
Cut rich benzene cut by the method for example 1, be 75 ~ 90 DEG C unlike cutting boiling range, obtain rich benzene cut 728g, benzene content is 40.27 volume %, and rich for 700g benzene cut and ethene are carried out alkylated reaction, and alkylation catalyst is MCM-22 molecular sieve.Controlling benzene/ethylene molecule ratio during reaction is 3: 1, and alkylated reaction temperature is 160 DEG C, pressure is 4.0MPa, the mass space velocity of ethene is 1.0h
-1.By example 1 method through three alkylideneization reaction after, benzene transformation efficiency is 70.8 quality %, and doing of the alkylate obtained is 215 DEG C, wherein C
9 +aromaticity content is 12.1 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts many ethylbenzene cut 20g of 160 ~ 220 DEG C, in described many ethylbenzene cut, diethylbenzene content is 45.4 quality %, triethyl-benzene content is 4.1 quality %.Be the rich benzene cut 28g of 75 ~ 90 DEG C by multi-ethyl phenenyl cut and boiling range, the micro-reactor passing into filling transalkylation catalyst carries out alkylated reaction, the molecular ratio controlling benzene and many ethylbenzene is 1.5: 1,220 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 5.7h under the condition of 3.5MPa
-1, reaction after product does 160 DEG C, diethylbenzene transformation efficiency 98 quality %, triethyl-benzene transformation efficiency 100 quality %.
The rich benzene cut of above-mentioned 75 ~ 90 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 7.60 volume %, remain after cut mixes with reformate cutting, benzene content is 0.86 volume %.
Example 4
Alkylation and transalkylation catalyst are MCM-22 molecular sieve, and silica/alumina molar ratio is 30.
(1) alkylated reaction is carried out
Rich benzene cut is cut by the method for example 1, unlike cutting boiling range be 75 ~ 90 DEG C, obtain rich benzene cut 706g, rich benzene cut benzene content is 40.27 volume %, rich for 700g benzene cut and propylene are carried out alkylated reaction, and alkylation catalyst is MCM-22 molecular sieve.Controlling benzene/propylene molecules ratio during reaction is 6: 1, and alkylated reaction temperature is 160 DEG C, pressure is 4.0MPa, the mass space velocity of propylene is 1.0h
-1.By example 1 method through three alkylideneization reaction after, benzene transformation efficiency is 30.2 quality %, and doing of the alkylate obtained is 210 DEG C, wherein C
9 +aromaticity content is 5.3 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts the polyisopropylbenzene cut 19g of 160 ~ 220 DEG C, wherein containing diisopropyl benzene 20.3 quality %, triisopropylbenzene 0.8 quality %.Be that rich benzene cut 6g and many cumene fraction 19g of 75 ~ 90 DEG C passes in the micro-reactor loading transalkylation catalyst by boiling range, the molecular ratio controlling benzene and polyisopropylbenzene is 1: 1.5,200 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 4.5h under the condition of 4.0MPa
-1.Reaction after product does 175 DEG C, many cumene rate 98 quality %.
The rich benzene cut of above-mentioned 75 ~ 90 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 23.62 volume %, remain after cut mixes with reformate cutting, benzene content is 3.21 volume %.
Example 5
Alkylation catalyst is MCM-22 molecular sieve, and silica/alumina molar ratio is 30, and transalkylation catalyst is AEB-1.
(1) alkylated reaction is carried out
Cut rich benzene cut by the method for example 1, be 75 ~ 90 DEG C, obtain rich benzene cut 716g unlike cutting boiling range, rich benzene cut benzene content is that the rich benzene cut of 40.27 volume %, 700g and propylene carry out alkylated reaction, and alkylation catalyst is MCM-22 molecular sieve.Controlling benzene/propylene molecules ratio during reaction is 3: 1, and alkylated reaction temperature is 180 DEG C, pressure is 3.0MPa, the mass space velocity of propylene is 1.2h
-1.By example 1 method through three alkylideneization reaction after, doing of the alkylate obtained is 210 DEG C, and benzene transformation efficiency is 68.9 quality %, wherein C
9 +aromaticity content is 12.8 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts out the polyisopropylbenzene cut 22g of 160 ~ 220 DEG C, wherein containing diisopropyl benzene 42.6 quality %, triisopropylbenzene 2.2 quality %.Be that rich benzene cut 16g and many cumene fraction 22g of 75 ~ 90 DEG C passes into the micro-reactor loading transalkylation catalyst by boiling range, the molecular ratio controlling benzene and polyisopropylbenzene is 1: 1.5,180 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 3.2h under the condition of 3.0MPa
-1.Reaction after product does 175 DEG C, polyisopropylbenzene transformation efficiency 97 quality %.
The rich benzene cut of above-mentioned 75 ~ 90 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 8.86 volume %, remain after cut mixes with reformate cutting, benzene content is 0.92 volume %.
Example 6
Alkylation catalyst is carried heteropoly acid catalyst, and heteropolyacid is H
3pW
12o
40, carrier α-Al
2o
3, loaded by heteropoly acid amount 20 quality %.Transalkylation catalyst is AEB-2.
(1) alkylated reaction is carried out
Rich benzene cut is cut by the method for example 1, unlike cutting boiling range be 70 ~ 90 DEG C, obtain rich benzene cut 732g, rich benzene cut benzene content is 30.18 volume %, the rich benzene cut of 700g and ethene carry out alkylated reaction, and alkylation catalyst is carried heteropoly acid catalyst.Controlling benzene/ethylene molecule ratio during reaction is 3: 1, and alkylated reaction temperature is 140 DEG C, pressure is 4.5MPa, the mass space velocity of ethene is 1.5h
-1.By example 1 method through three alkylideneization reaction after, doing of the alkylate obtained is 210 DEG C, and benzene transformation efficiency is 50.6 quality %, wherein C
9 +aromaticity content is 6.2 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts out many ethylbenzene cut 25g of 160 ~ 220 DEG C, in described many ethylbenzene cut, diethylbenzene content is 40.5 quality %, triethyl-benzene content is 7.1 quality %.Be that the rich benzene cut 32g of 70 ~ 90 DEG C and many cumene fraction 25g pass into the micro-reactor loading transalkylation catalyst and carry out alkylated reaction by boiling range, the molecular ratio controlling benzene and many ethylbenzene is 1.5: 1,180 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 8.1h under the condition of 3.0MPa
-1, reaction after product does 175 DEG C, diethylbenzene transformation efficiency 95 quality %, triethyl-benzene transformation efficiency 100 quality %.
The rich benzene cut of above-mentioned 70 ~ 90 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 13.20 volume %, remain after cut mixes with reformate cutting, benzene content is 1.56 volume %.
Example 7
Alkylation catalyst is AEB-2, and transalkylation catalyst is AEB-1.
(1) alkylated reaction is carried out
Cut rich benzene cut 713g by the method for example 1, rich for 700g benzene cut and propylene are carried out alkylated reaction, and alkylation catalyst is AEB-2.Controlling benzene/propylene molecules ratio during reaction is 6: 1, and alkylated reaction temperature is 180 DEG C, pressure is 3.0MPa, the mass space velocity of propylene is 1.0h
-1.By example 1 method through three alkylideneization reaction after, doing of the alkylate obtained is 192 DEG C, and benzene transformation efficiency is 28.3 quality %, wherein C
9 +aromaticity content is 2.4 quality %.
(2) transalkylation reaction is carried out
Third time alkylation products therefrom is carried out rectifying, cuts out the polyisopropylbenzene cut 18g of 160 ~ 220 DEG C, wherein containing diisopropyl benzene 30.1 quality %, triisopropylbenzene 2.3 quality %.Be that rich benzene cut 13g and many cumene fraction 18g of 65 ~ 95 DEG C passes in the micro-reactor loading transalkylation catalyst by boiling range, the molecular ratio controlling benzene and polyisopropylbenzene is 1: 1,220 DEG C, carry out transalkylation reaction, rich benzene cut mass space velocity 6.7h under the condition of 3.0MPa
-1.Reaction after product does 173 DEG C, many cumene rate 97 quality %.
The rich benzene cut of above-mentioned 65 ~ 95 DEG C is after aforesaid method process, transalkylation reaction product and the benzene content that the alkylate being less than 160 DEG C merges the mixture obtained are down to 13.60 volume %, remain after cut mixes with reformate cutting, benzene content is 2.62 volume %.
Claims (11)
1. reduce a method for benzene content in reformed oil, comprise the rich benzene cut of reformed oil and C
2~ C
4alkene contact under the existence of alkylation catalyst and carry out alkylated reaction, polyalkylbenzene cut in alkylation reaction product is contacted in the presence of a transalkylation catalyst with the rich benzene cut of reformed oil and carries out transalkylation reaction, the rich benzene cut of described reformed oil is that in reformed oil, boiling range is the cut of 60 ~ 95 DEG C, wherein benzene content is 20 ~ 50 volume %, and the initial boiling point of the polyalkylbenzene cut in alkylation reaction product is 160 ~ 180 DEG C.
2. the boiling range that in accordance with the method for claim 1, it is characterized in that described rich benzene cut is 75 ~ 90 DEG C.
3. in accordance with the method for claim 1, it is characterized in that the temperature of alkylated reaction is 100 ~ 300 DEG C, pressure is 0.1 ~ 6.0MPa.
4. in accordance with the method for claim 1, it is characterized in that described C
2~ C
4alkene be selected from ethene, propylene or butylene.
5. in accordance with the method for claim 1, it is characterized in that the benzene in alkylation process in rich benzene cut and C
2~ C
4the molecular ratio of alkene is 1 ~ 8.
6. in accordance with the method for claim 1, it is characterized in that the temperature of described transalkylation reaction is 120 ~ 350 DEG C, pressure is 0.1 ~ 6.0MPa.
7. in accordance with the method for claim 1, it is characterized in that in transalkylation reaction, the molecular ratio of the benzene in rich benzene cut and the polyalkylbenzene in polyalkylbenzene cut is 0.6 ~ 7.5.
8. in accordance with the method for claim 1, it is characterized in that described alkylation catalyst and transalkylation catalyst are selected from acidic zeolite or heteropolyacid.
9. in accordance with the method for claim 8, it is characterized in that one or more that acidic zeolite is selected from MFI, FAU, MOR, MWW, MTW, TON, MTT, MEL, FER, EON, BEA, AFI, MAZ, IWW and NES structural zeolite.
10. in accordance with the method for claim 8, it is characterized in that described alkylation catalyst is selected from β, ZSM-5, MCM-22, mordenite, ITQ-2, MCM-36, MCM-49, MCM-56 zeolite or heteropolyacid, described transalkylation catalyst is selected from Y, USY, MCM-22, MCM-36, MCM-49 or MCM-56 zeolite.
11. in accordance with the method for claim 1, it is characterized in that the content of polyalkylbenzene in polyalkylbenzene cut is 20 ~ 60 quality %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110109863.9A CN102757815B (en) | 2011-04-29 | 2011-04-29 | A kind of method reducing benzene content in reformed oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110109863.9A CN102757815B (en) | 2011-04-29 | 2011-04-29 | A kind of method reducing benzene content in reformed oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102757815A CN102757815A (en) | 2012-10-31 |
| CN102757815B true CN102757815B (en) | 2015-09-23 |
Family
ID=47052469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110109863.9A Active CN102757815B (en) | 2011-04-29 | 2011-04-29 | A kind of method reducing benzene content in reformed oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102757815B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772066B (en) * | 2014-12-22 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of catalyst and preparation method thereof being used to prepare bi-end-blocking glycol ether |
| CN107790172B (en) * | 2016-08-30 | 2020-07-07 | 中国石油化工股份有限公司 | Transalkylation catalyst, process for its preparation and use |
| CN110498725B (en) * | 2018-05-16 | 2022-03-11 | 中国石油化工股份有限公司 | Solid acid catalyzed alkylation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552811A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Method for decreasing benzene concentration of gasoline |
| CN101451076A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for reducing benzene content in gasoline |
-
2011
- 2011-04-29 CN CN201110109863.9A patent/CN102757815B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552811A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Method for decreasing benzene concentration of gasoline |
| CN101451076A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for reducing benzene content in gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102757815A (en) | 2012-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103168088B (en) | High-octane rating alkylide is produced by ethene and Trimethylmethane | |
| JP4958799B2 (en) | Liquid phase aromatic alkylation process | |
| US3549557A (en) | Isoparaffin alkylation process and catalyst for use therein | |
| CN101062879B (en) | Coking benzene deep desulfuration purification method | |
| CN1918088A (en) | Hydrocarbon alkylation conversion method using nanocrystalline zeolite y | |
| CN102387861A (en) | Catalysts useful for the alkylation of aromatic hydrocarbons | |
| CN101116827B (en) | Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking and its uses | |
| CN101910094A (en) | Process for the conversion of ethane or mixed lower alkanes to aromatic hydrocarbons | |
| JP2010515746A (en) | Dual zone alkylation process for aromatic compounds | |
| KR100517593B1 (en) | Catalysts and methods for the conversion of aromatic hydrocarbons and their use in the production of aromatic hydrocarbons | |
| CN101376823A (en) | Benzin naphtha catalytic reforming method | |
| CN1834075B (en) | Process for the co-production of cumene and secondary butyl benzene | |
| CN107754845B (en) | Long-life catalyst for reducing olefins in reformate | |
| CA3044551A1 (en) | Method for converting hydrocarbons including conversion of a hydroperoxide to an alcohol and production of alkylate from an isoparaffin feed | |
| CA2858726A1 (en) | Aromatic transformation using uzm-39 aluminosilicate zeolite | |
| CN102757815B (en) | A kind of method reducing benzene content in reformed oil | |
| CN101451076A (en) | Method for reducing benzene content in gasoline | |
| CN101279280B (en) | Catalyst for preparing propylene transformed from methanol | |
| JP2014513152A (en) | Method for reducing the benzene content of gasoline | |
| CN102807465B (en) | Method for producing propane and gasoline by using butane | |
| CN102069008B (en) | Catalyst for removing olefin in reformed arene and preparation method thereof | |
| CN102757816B (en) | Benzene reducing method of reformate | |
| CA2599503A1 (en) | Vapor phase aromatics alkylation process | |
| Borutskii et al. | Alkylation of benzene with higher olefins on heterogeneous catalysts | |
| US20200291303A1 (en) | Method and catalyst for producing high octane components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |