CN107473925A - A kind of method that ethylbenzene is prepared using low-carbon alkanes - Google Patents
A kind of method that ethylbenzene is prepared using low-carbon alkanes Download PDFInfo
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- CN107473925A CN107473925A CN201710804426.6A CN201710804426A CN107473925A CN 107473925 A CN107473925 A CN 107473925A CN 201710804426 A CN201710804426 A CN 201710804426A CN 107473925 A CN107473925 A CN 107473925A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The present invention provides a kind of method that ethylbenzene is prepared using low-carbon alkanes, comprises the following steps：(1) logistics containing low-carbon alkanes is mixed with steam to be sent into cracker and carries out cracking reaction, obtain the cracking gas rich in alkene；(2) cracking gas is sent into alkaline cleaner and removes sour gas therein, the cracking gas after being purified；(3) cracking gas after the purification is sent into cracking gas separative element, ethylene-rich gas is isolated in cracking gas separative element；(4) the ethylene-rich pneumatic transmission is entered into acetylene conversion reaction device and removes alkynes therein；(5) the ethylene-rich pneumatic transmission of benzene and removing alkynes is entered into alkylation reaction device and carries out alkylation reaction, alkylation reaction product is sent into ethylbenzene separative element, ethylbenzene is isolated in ethylbenzene separative element.The method provided by the invention that ethylbenzene is prepared using low-carbon alkanes, has effectively expanded the utilization ways of low-carbon alkanes, hews out the ethylbenzene independently of ethylene plant/oil plant and produces path.
Description
Technical field
The present invention relates to a kind of method for preparing ethylbenzene by the means such as cracking, being alkylated using low-carbon alkanes.
Background technology
Low-carbon alkanes are mainly derived from the byproduct of refinery's process, oil field liquefied gas, liquefied gas inlet and ethane etc.,
Its main component includes ethane, propane, iso-butane and normal butane.
At present, in refinery, mainly there are following several ways for the industrial utilization of low-carbon alkanes：First, by second therein
Alkane is used as fuel gas；Second, propane therein and butane are sold as low value liquefied gas.Also there are a small number of refineries by lower alkanes
Hydrocarbon is separated, and isolated pure component is used respectively.Mainly Land use systems are：By the pure component dehydrogenation system of separation
Corresponding alkene, such as preparing propylene by dehydrogenating propane, separate after preparing isobutene through dehydrogenation of iso-butane, or the two mixing dehydrogenation.But due to
The economic scale of the technical requirements is of a relatively high, causes the collection buying of its raw material limited larger.Such as dehydrogenating propane device
Economic scale is typically not less than 250,000 tons/year of propylene.On the other hand, with the requirement that oil product upgrades, to the need of alkyl plant
Increase is asked, and iso-butane can obtain certain application in this respect as the raw material of alkyl plant, but its application is also by oil
The influence of this main trend of product surplus.It is relatively fewer to the Application way of normal butane, typically it is isomerized to iso-butane and is added again
To utilize.
It is well known that ethylbenzene is a kind of important industrial chemicals, it is mainly used in the production of styrene.The industrial production of ethylbenzene
Method mainly has two kinds, is dry gas method and high-purity ethylene method respectively.Wherein, dry gas method uses the dry gas of refinery catalytic cracking device
With benzene preparing ethylbenzene by reaction, but this method is limited to the yield of catalysis drying gas, the ethylbenzene scale is smaller of such device is caused, to ethylbenzene
The influence power in market is smaller.Disclosed in Publication No. CN103772125A Chinese patent application it is a kind of using oil refinery dry gas as
Dry gas from refinery facilities is introduced oily absorption plant by the method for waste ethylbenzene, this method, and recovered, concentrate obtains carbon
Two concentrate gas, then by being hydrogenated with, be alkylated, and benzene reaction production ethylbenzene product.The main purpose of this method is proposition one
The method that kind efficiently produces ethylbenzene using the ethene in oil refinery dry gas, ethane component.
In addition, high-purity ethylene rule need to use the ethene and benzene preparing ethylbenzene by reaction of high-purity, because high-purity ethylene can only
Come from ethylene plant, but the transport of ethene is extremely difficult；So corresponding second is typically relied on using the Benzene Device of the technique
Alkene factory, this virtually improves the entry threshold in ethylbenzene market.
The content of the invention
The present invention is to make up the deficiencies in the prior art, there is provided a kind of method that ethylbenzene is prepared using low-carbon alkanes,
So as to effectively expand the utilization ways of low-carbon alkanes, the ethylbenzene hewed out independently of ethylene plant/oil plant produces path.
For the present invention to reach its purpose, the technical scheme of use is as follows：
A kind of method that ethylbenzene is prepared using low-carbon alkanes, is comprised the following steps：
(1) logistics containing low-carbon alkanes is mixed with steam to be sent into cracker and carries out cracking reaction, be rich in
The cracking gas of alkene；
(2) cracking gas is sent into alkaline cleaner and removes sour gas therein, the cracking gas after being purified；
(3) cracking gas after the purification is sent into cracking gas separative element, Fu Yi is isolated in cracking gas separative element
Alkene gas；
(4) the ethylene-rich pneumatic transmission is entered into acetylene conversion reaction device and removes alkynes therein；
(5) the ethylene-rich pneumatic transmission of benzene and removing alkynes is entered into alkylation reaction device and carries out alkylation reaction, alkylation reaction is produced
Thing is sent into ethylbenzene separative element, and ethylbenzene is isolated in ethylbenzene separative element.
In the present invention, the logistics containing low-carbon alkanes, it, which is formed, has no particular/special requirement, in implementation process, and is not required to
It is separated in advance, caused energy consumption in separation process can be reduced.And as a kind of preferred scheme in the present invention, step
Suddenly the low-carbon alkanes described in (1) are preferably the alkane of carbon number 2-6 alkane, more preferably carbon number 2-4, such as second
Alkane, propane, iso-butane and normal butane etc..On the other hand, the low-carbon alkanes described in step (1) of the present invention can derive from saturation
Liquefied gas or ethane, other forms for being likely to become low-carbon alkanes source are also not excluded for certainly.
In the step (1) of the present invention, at least one in ethene, propylene is preferably comprised in the cracking gas rich in alkene
Kind.
As the preferred scheme of the present invention, in step (1), the mass ratio of the steam and the air-flow containing low-carbon alkanes is
0.3-0.5；Condition when cracking reaction is carried out in cracker preferably includes：Temperature is 860-880 DEG C, pressure 0.18-
0.25MPa, volume space velocity 18000-24000h-1。
As the preferred scheme of the present invention, in step (1), after the logistics containing low-carbon alkanes and steam mixing, add
Hot to 670-730 DEG C is re-fed into the cracker；The cracking gas boosts to 1-1.4MPa before alkaline cleaner is sent into,
And temperature control is to 45-50 DEG C.
As a kind of embodiment of the present invention, after cracking gas is sent into alkaline cleaner, removed by alkali cleaning and water elution
Sour gas therein.
As the preferred scheme of the present invention, in step (3), after the cracking gas after the purification boosts to 2-2.2MPa, then
It is sent into cracking gas separative element；In step (4), the ethylene-rich gas is warming up to 60-65 DEG C and is re-fed into the acetylene conversion reaction
Device.
In the embodiment of the present invention, when ethylene-rich pneumatic transmission enters to remove alkynes in acetylene conversion reaction device, institute
Catalyst is the industrial ripe acetylene reforming catalyst in this area, and the supplier such as example, Ke Laien, shell CRI produces
Corresponding catalyst.
Currently preferred, in step (5), the condition of the alkylation reaction includes：320-370 DEG C of reaction temperature, reaction
Pressure 0.85-1.5MPa, benzene ethylene molecular proportion 5-7, weight ethylene air speed 0.2-0.8h-1。
In a preferred embodiment of the invention, in step (5), the benzene is heated to before being sent into alkylation reaction device
320-370℃.In the scheme that the present invention is more highly preferred to, in addition to following operation：It is hot caused by cracking reaction in recycling step (1)
The raw material for being sent into alkylation reaction device in heating stepses (5) is measured, raw material is heated extremely by the heat or auxiliary of recovery
Required reaction temperature, reach energy-conserving and environment-protective, reduce the purpose of cost.
In the preferred scheme of the present invention, in step (5), the alkylation reaction product is isolated through the ethylbenzene separative element
Material include more ethylbenzene, such as the component such as diethylbenzene, triethylbenzene (TEB), more ethylbenzene are sent into dealkylation reaction devices and entered with benzene
Row dealkylation reaction, products therefrom are re-fed into the ethylbenzene separative element and isolate ethylbenzene therein.
Currently preferred, the condition of the dealkylation reaction includes：220-260 DEG C of reaction temperature, reaction pressure 3.3-
3.8MPa, benzene/more ethylbenzene weight ratios are 5-7, weight space velocity 1.5-2.0h-1。
In a kind of preferred embodiment of the present invention, the ethylbenzene separative element includes crude tower, benzene column, ethylbenzene tower, institute
State alkylation reaction product and be sent into crude tower, fixed gas is isolated by the tower top of crude tower, the materials at bottom of tower of crude tower is sent into benzene column；
Fixed gas (for the fixed gas containing benzene) is isolated by benzene column tower top, the material of benzene column bottom is sent into ethylbenzene tower；By the top of ethylbenzene tower
Part separates out ethylbenzene.
In further preferred embodiment of the present invention, the ethylbenzene separative element also includes propyl benzene tower, diethyl benzene column, institute
The bottoms material for stating ethylbenzene tower is sent into propyl benzene tower, and by isolating propyl benzene at the top of propyl benzene tower, the material of propyl benzene tower bottom is sent into two
Ethylbenzene tower；By isolating more ethylbenzene at the top of diethyl benzene column.
In further preferred embodiment of the present invention, the ethylbenzene separative element also includes absorption tower, the diethylbenzene
The material parts isolated at the top of tower or whole feeding absorption towers, the fixed gas that crude tower is isolated is sent into absorption tower, by institute
The tower top for stating absorption tower isolates fuel gas, and the material at absorbing tower bottom is sent into dealkylation reaction device.
In the preferred embodiment of the present invention, dealkylation reaction product is fed through the benzene column.
In a kind of preferred embodiment of the present invention, in step (3), the cracking gas separative element includes cracking aspiration
Tower, the cracking gas after the purification are entered in tower by the middle part on cracking gas absorption tower or middle and lower part, the top with cracking gas absorption tower
The solvent contact that subordinate comes, ethylene-rich gas is obtained by top of tower.Preferably, the solvent to get off at the top of the cracking gas absorption tower
For heavy aromatics.
In the preferred embodiment of the present invention, it is further preferred that the cracking gas separative element also includes depropanizing tower,
The material of cracking gas absorb the bottom of the tower is sent into depropanizing tower, and the component of carbon three is obtained by the tower top of depropanizing tower.
In the preferred embodiment of the present invention, it is further preferred that the component of the carbon three is sent into the removing of alkynes reaction unit
Alkynes therein, propylene and propane are isolated from the material after removing alkynes.
It is further preferred that in cracker in the propane cycles to step (1).
In the preferred embodiment of the present invention, drippolene is also isolated by the depropanizing tower, the drippolene
Cracking gas absorption tower partly or entirely is fed through, and cracking gas absorption tower is entered by the middle part on cracking gas absorption tower or middle and upper part
It is interior, used as solvent.
In the preferred embodiment of the present invention, the cracking gas separative element also includes deheptanizer, by the depropanization
The part drippolene that tower separation obtains delivers to the deheptanizer, drippolene is obtained by the tower top of deheptanizer, by taking off heptan
The bottom of towe of alkane tower obtains heavy aromatics component, and the heavy aromatics component is sent into the top on cracking gas absorption tower, used as solvent.
In the preferred embodiment of the present invention, the cracking gas separative element also includes debutanizing tower, by the depropanization
Tower also isolates the component of carbon four, and the component of carbon four is sent into debutanizing tower, is obtained by the tower top separation of debutanizing tower and is rich in fourth two
The component of carbon four of alkene, drippolene is obtained by the bottom of towe of debutanizing tower.
Technical scheme provided by the invention has the advantages that：
The present invention has widened the utilization ways of low-carbon alkanes (particularly normal butane), realizes low-carbon alkanes (particularly positive fourth
Alkane) efficient utilization, while the ethylbenzene opened independently of ethylene plant/oil plant produces path, carries for corresponding industrial user
For more selections.The cracking product of the present invention can be reduced effectively without preparing dense ethene by cryogenic separation process
Journey energy consumption.
The present invention wants to the strong adaptability of raw material to the composition of low-carbon alkanes raw material (particularly saturation liquefied gas) without special
Ask, and do not require to separate it in advance, reduce energy consumption caused by separation process.
Ethylene-rich gas of the present invention and benzene alkylation (alkylation reaction) process, take off propylene without setting dry gas compression unit and dry gas
Unit, and using unit (cracking reaction) recovery heat alkylation process raw material is cracked, without setting recycle benzene heating furnace, have
Effect reduces alkylation process investment and energy consumption.
The present invention is to requirement of the equipment without special substance, and no Cryo Equipment, device design scale is flexible, elastic range compared with
Greatly, and beneficial to compact production space is reached design.
Brief description of the drawings
Fig. 1 is the technological process of production sketch in the embodiment of the present invention.
Embodiment
In order to be better understood from technical scheme, present disclosure is expanded on further with reference to embodiment,
But present disclosure is not limited only to following examples.
In the examples below, used process chart can be found in Fig. 1.
Embodiment 1
Using the low-value product saturation liquefied gas LPG in refinery as raw material, 100,000 tons/year of ethylbenzene are produced.
The raw materials used composition of the present embodiment is as shown in table 1 below：
Table 1
| Composition | Wt% |
| Propane | 20 |
| Normal butane | 50 |
| Iso-butane | 30 |
| It is total | 100 |
The consumption of raw materials of the present embodiment is as shown in table 2 below：
Table 2
| Raw material | KTA | kg/hr |
| LPG | 80 | 10005 |
| Benzene | 72 | 8996 |
| It is total | 152 | 19001 |
The technological condition of the present embodiment is as shown in table 3 below：
Table 3
The technique of the present embodiment production ethylbenzene is as follows：
(1) unit is cracked：
By normal temperature saturation liquefied gas that pressure is 1.5MPa or so, (in continuous flow procedure, the saturation liquefied gas can be with
Merge with caused recycled propane in later step), vaporizer is entered after chilled water (chw) preheats, all again will with steam after gasification
It is superheated to about 180 DEG C.Convection section in cracking furnace heating is sent into after being mixed with steam in the lump, is heated to about 700 DEG C of (670-730
DEG C), cracking reaction then occurs into the cracking furnace pipe of pyrolysis furnace radiant section, pyrolysis product is rich in alkene such as ethene, propylene
The gas (the referred to as cracking gas rich in alkene) of hydrocarbon.
The temperature that cracking gas goes out radiant section is about 865 DEG C, 240 °C or so is cooled to through two sections of rapid-cooling heat exchangers, under
The further lowered temperature reclamation heat of chilling tower of trip.Two sections of rapid-cooling heat exchangers are used to steam occur to reclaim the heat of cracking gas, steam
The grade of vapour can be extra high pressure steam (10MPa or so) or high steam (4MPa or so), be determined by the demand of full factory.
Crack heating of the heat of unit recovery for the raw material in follow-up alkylation reaction such as recycle benzene, ethylene-rich gas.
Cracking gas chilling and compression unit：
Cracking gas from pyrolysis furnace enters quenching water column, and under the direct cooling of chilled water (chw), temperature is further reduced to about
40 DEG C (35-45 DEG C), are boosted into compressor assembly.The heat that chilled water (chw) absorbs sends to low temperature user, such as propylene rectifying
Tower reboiler, liquefied gas feed preheater etc. are recycled.Compressor assembly specifically compresses using level Four, the fourth stage
Positioned at cracking gas impurity removing unit.Cracking gas after cooling boosts to about 1.2MPa (1-1.4MPa) through three stage compression.Compressor machine
Between condense under liquid after water-oil separating, the lower oil phase of oil phase and chilling tower condensation is sent into gasoline stripping tower in the lump, obtains surely
Fixed drippolene carrying device.
(2) cracking gas impurity removing unit：
Cracking gas impurity removing unit is mainly to remove the acidic components in cracking gas, such as H2S,CO2Deng.Cracking after boosted
Gas is preheated to 45 DEG C or so (45-50 DEG C) feeding caustic wash towers through chilled water (chw), after three sections of alkali cleanings and top washing, by acid qi exhaustion
Remove, the cracking gas after purification boosts to about 2.1MPa (2-2.2MPa) in the charge gas compressor fourth stage and is sent into follow-up cracking afterwards
Gas separative element.The sulfur content and the processing capacity of raw material that the growing amount of spent lye is depended in raw material.
(3) cracking gas separative element
Cracking gas after purification enters cracking gas absorption tower.The operating pressure on cracking gas absorption tower is about 2.0MPa.
Cracking gas enters from the middle and lower part on cracking gas absorption tower, is contacted with the solvent that top is got off, carbon three and heavier group
Divide with solvent to tower lower flow, carbon two and lighter component obtain ethylene-rich gas row to tower upper flow, and then in top of tower
Go out.Used solvent has two kinds, enters cracking gas absorption tower from top of tower and tower middle and upper part respectively, and the solvent at top is attached most importance to virtue
Hydrocarbon, the solvent of middle and upper part are the drippolene that follow-up depropanizing tower bottom is isolated.
The materials at bottom of tower on cracking gas absorption tower is sent into depropanizing tower, and the operating pressure of depropanizing tower is about 1.6MPa.De-
Propane tower top obtains the product of carbon three (or being the component of carbon three), sends to alkynes reactor removing alkynes, then enters into propylene tower
One step separates.Alkynes reactor is using industrial ripe alkynes reforming catalyst, such as shell CRI KL catalyst series.Third
Alkene tower is operated using cascade towers, and operating pressure is about 1.9MPa.Tower top obtains polymerization-grade propylene product, carrying device.Bottom of towe
Bromopropane product is obtained, pyrolysis furnace is sent to and recycles.
Whole components of carbon four sends to debutanizing tower in the middle and lower part side take-off of depropanizing tower.Debutanizing tower is conventional
Plate column, operating pressure is about 0.5MPa.Tower top obtains the component of mixing carbon four (or referred to as four groups of the carbon rich in butadiene
Point, it is designated as mixing carbon four in Fig. 1), carrying device.Bottom of towe is light petrol component (or being drippolene), is stripped with gasoline
Carrying device after bottom product merges.
The drippolene that depropanizing tower bottom of towe obtains, about 90% is recycled back in the feed side of cracking gas absorption tower after cooling
Portion uses as solvent, and remainder sends to deheptanizer.Deheptanizer is conventional plate column, and operating pressure is about
0.2MPa.The tower top of deheptanizer obtains light petrol component (or being drippolene) and merges submitting with gasoline stripping tower bottom product
Device.Bottom of towe is attached most importance to aromatic component, and the top for sending to cracking gas absorption tower after cooling uses as solvent.
(4) alkynes is removed
Cracking gas absorption tower tower top discharge ethylene-rich gas through further heating up to about 60 DEG C (60-65 DEG C), it is laggard
Enter acetylene conversion reactor and remove alkynes therein, then send to alkylation reaction unit.The catalyst of acetylene conversion reactor is adopted
With industrial ripe catalyst, can specifically be urged using Ke Laien OleMax catalyst series or shell CRI KL series
Agent.
(5) alkylation reaction unit
Fresh benzene is sent into recycle benzene surge tank, is mixed with the recycle benzene from crude tower and benzene column lateral line withdrawal function, after heat exchange
Into recycle benzene heating furnace, 320 DEG C are heated to, into alkylation reaction device top.
The cracking qi leel multichannel of removing alkynes enters alkylation reaction device, and gas phase alkylation reaction occurs.
Alkylation reaction condition：320-370 DEG C of reaction temperature, 0.85-1.5MPa, benzene ethylene molecular proportion 5-7, weight ethylene
Air speed 0.2-0.8.Alkylation reaction device 2-3 platforms, the operation of 1-2 platforms, another 1 regeneration, 360-410 DEG C of alkylation reaction product, 0.85-
1.5MPa。
Ethylbenzene separative element：
Alkylation reaction product after heat exchange enters crude tower, and fixed gas of the tower top by condensation enters absorption tower, bottoms
Enter benzene column after material heat exchange.Fixed gas containing benzene is steamed from benzene column tower top, and the materials at bottom of tower of benzene column is pressed into ethylbenzene tower certainly.
The material come from benzene column bottom of towe enters ethylbenzene tower, and ethylbenzene steams from tower top, and materials at bottom of tower pressurizes through ethylbenzene column bottoms pump
Enter propyl benzene tower afterwards.
The material come from ethylbenzene tower bottom enters propyl benzene tower, and propyl benzene steams from tower top, and propyl benzene materials at bottom of tower is through propyl benzene column bottoms pump
It is sent into diethyl benzene column.
After the charging of diethyl benzene column enters diethyl benzene column, more ethylbenzene components such as diethylbenzene, triethylbenzene (TEB) steam from tower top, into two
Ethylbenzene tower top condensate cooler condenses, and condensate liquid enters diethyl benzene column return tank, and about 1/3 condensate liquid is through diethylbenzene overhead reflux
Pump is returned to flow back in tower, and another part enters absorption tower.The bottom of towe of diethyl benzene column is high-boiling components, and high-boiling components are through diethyl benzene column tower
Bottom is pumped into tank sending area after the cooling of high-boiling components cooler.The material at absorbing tower bottom enters dealkylation reaction device, and tower top isolates combustion
Expect gas.
(6) dealkylation reaction unit
The material (more ethylbenzene) that the bottom of self-absorption tower is come is boosted to after being mixed with benzene by dealkylation reaction feed pump
3.8MPaG, it is heated to 220 DEG C through dealkylation reaction feed heater and enters dealkylation reaction device.Come out by dealkylation reaction device
Reverse alkylation product enter benzene column.
Dealkylation reaction condition：220-260 DEG C of reaction temperature, reaction pressure 3.3-3.8MPa, benzene/more ethylbenzene weight ratios are
5-7, dealkylation reaction device 1,220-260 DEG C of dealkylation reaction product, 3.3-3.8MPa.
The product distribution of the present embodiment is as shown in table 4 below：
Table 4
| Product | KTA | kg/hr |
| Fuel gas | 24 | 3041 |
| Propylene | 16 | 2000 |
| Mix C 4 olefin | 7 | 828 |
| Drippolene | 4 | 309 |
| Ethylbenzene | 100 | 12500 |
| Propyl benzene | 1 | 140 |
| High-boiling components | 0.2 | 31 |
| It is total | 152 | 19001 |
Consider the circulation of propane/butane in table 3, and in drippolene benzene recovery.Mix the fourth two in C 4 olefin
Alkene is removed because content is less using selective hydrogenation.
Embodiment 2
The present embodiment is raw material from normal butane, produces 300,000 tons/year of ethylbenzene.The process of the present embodiment is with reference to implementation
Example 1, is repeated no more.
The raw materials used composition of the present embodiment is shown in Table 5：
Table 5
| Composition | Wt% |
| Normal butane | 100 |
| It is total | 100 |
The consumption of raw materials of the present embodiment is shown in Table 6.
Table 6
| Raw material | KTA | kg/hr |
| Normal butane | 195 | 24392 |
| Benzene | 219 | 27381 |
| It is total | 414 | 51772 |
The product distribution of the present embodiment is shown in Table 7.
Table 7
| Product | KTA | kg/hr |
| Fuel gas | 58 | 7227 |
| Propylene | 36 | 4442 |
| Mix C 4 olefin | 11 | 1323 |
| Wherein butadiene | 7 | 866 |
| Drippolene | 6 | 768 |
| Ethylbenzene | 300 | 37500 |
| Propyl benzene | 3 | 419 |
| High-boiling components | 1 | 93 |
| It is total | 414 | 51772 |
Consider the circulation of propane/normal butane in table 7, and in drippolene benzene recovery.
The technological condition of the present embodiment is shown in Table 8.
Table 8
From the present embodiment, for the supporting more complete refinery of oil refining apparatus, the present invention can effectively utilize just
Butane resource, and do not need newly-built ethylene unit can to produce ethylbenzene fairly largely, effectively expand the business neck of enterprise
Domain.
Embodiment 3
The present embodiment is raw material from ethane, produces 600,000 tons/year of ethylbenzene.The process of the present embodiment is with reference to embodiment
1, repeat no more.
The raw material of the present embodiment is formed referring to table 9.
Table 9
| Composition | Wt% |
| Methane | 1.26 |
| Ethane | 93.77 |
| Propane | 4.97 |
| It is total | 100 |
The consumption of raw materials of the present embodiment is referring to table 10.
Table 10
| Raw material | KTA | kg/hr |
| Ethane | 311 | 38860 |
| Benzene | 448 | 55946 |
| It is total | 758 | 94806 |
The product of the present embodiment is distributed referring to table 11.
Table 11
Consider the circulation of propane/butane in table 11, and in drippolene benzene recovery.
The technological condition of the present embodiment is referring to table 12.
Table 12
From the present embodiment, using ethane and benzene as raw material, ethylbenzene is produced, it is not necessary to refinery and ethylene plant are relied on, can be with
Independently found the factory.Can selectively it be processed for byproduct, part byproduct can handle Posterior circle utilization, maximize production second
Benzene.
It will be understood by those skilled in the art that under the teaching of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (23)
- A kind of 1. method that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that comprise the following steps：(1) logistics containing low-carbon alkanes is mixed with steam to be sent into cracker and carries out cracking reaction, acquisition is rich in alkene Cracking gas；(2) cracking gas is sent into alkaline cleaner and removes sour gas therein, the cracking gas after being purified；(3) cracking gas after the purification is sent into cracking gas separative element, ethylene-rich gas is isolated in cracking gas separative element；(4) the ethylene-rich pneumatic transmission is entered into acetylene conversion reaction device and removes alkynes therein；(5) the ethylene-rich pneumatic transmission of benzene and removing alkynes is entered into alkylation reaction device and carries out alkylation reaction, alkylation reaction product is sent Enter ethylbenzene separative element, ethylbenzene is isolated in ethylbenzene separative element.
- 2. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (1) Low-carbon alkanes be carbon number 2-6 alkane, preferably carbon number 2-4 alkane.
- 3. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (1) Low-carbon alkanes derive from saturation liquefied gas or ethane.
- 4. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (1) Contain at least one of ethene, propylene in cracking gas rich in alkene.
- 5. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (1) Steam and the mass ratio of the logistics containing low-carbon alkanes are 0.3-0.5；Condition when cracking reaction is carried out in cracker includes：Temperature is 860-880 DEG C, pressure 0.18-0.25MPa, Volume space velocity is 18000-24000h-1。
- 6. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (1) After logistics containing low-carbon alkanes and steam mixing, it is heated to 670-730 DEG C and is re-fed into the cracker；The cracking gas exists It is sent into before alkaline cleaner, boosts to 1-1.4MPa, and temperature control is to 45-50 DEG C.
- 7. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (3) After cracking gas after purification boosts to 2-2.2MPa, cracking gas separative element is re-fed into；In step (4), the ethylene-rich gas lift Warm to 60-65 DEG C is re-fed into the acetylene conversion reaction device.
- 8. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (5) The condition of alkylation reaction includes：320-370 DEG C of reaction temperature, reaction pressure 0.85-1.5MPa, benzene ethylene molecular proportion 5-7, second Alkene weight space velocity 0.2-0.8h-1。
- 9. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that described in step (5) Benzene is heated to 320-370 DEG C before being sent into alkylation reaction device；Preferably, heat caused by cracking reaction in recycling step (1) For being sent into the raw material of alkylation reaction device in heating stepses (5).
- 10. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that in step (5), institute Stating the material that alkylation reaction product is isolated through the ethylbenzene separative element includes more ethylbenzene, and more ethylbenzene are sent into reverse alkylation Reaction unit carries out dealkylation reaction with benzene, and products therefrom is re-fed into the ethylbenzene separative element and isolates ethylbenzene therein.
- 11. the method according to claim 10 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the reverse alkylation is anti- The condition answered includes：220-260 DEG C of reaction temperature, reaction pressure 3.3-3.8MPa, benzene/more ethylbenzene weight ratios are 5-7, and weight is empty Speed is 1.5-2.0h-1。
- 12. the method according to claim 10 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the ethylbenzene separation Unit includes crude tower, benzene column, ethylbenzene tower, and the alkylation reaction product is sent into crude tower, isolated not by the tower top of crude tower Solidifying gas, the materials at bottom of tower of crude tower are sent into benzene column；Fixed gas is isolated by benzene column tower top, the material of benzene column bottom is sent into ethylbenzene Tower；By isolating ethylbenzene at the top of ethylbenzene tower.
- 13. the method according to claim 12 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the ethylbenzene separation Unit also includes propyl benzene tower, diethyl benzene column, and the bottoms material of the ethylbenzene tower is sent into propyl benzene tower, by being isolated at the top of propyl benzene tower Propyl benzene, the material of propyl benzene tower bottom are sent into diethyl benzene column；By isolating more ethylbenzene at the top of diethyl benzene column.
- 14. the method according to claim 13 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the ethylbenzene separation Unit also includes absorption tower, all material parts isolated at the top of the diethyl benzene column or feeding absorption tower, crude tower point The fixed gas separated out is sent into absorption tower, isolates fuel gas by the tower top on the absorption tower, the material at absorbing tower bottom is sent into instead Alkylation reaction device.
- 15. the method according to claim 12 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that dealkylation reaction produces Thing is fed through the benzene column.
- 16. the method according to claim 1 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that in step (3), institute Stating cracking gas separative element includes cracking gas absorption tower, the cracking gas after the purification by cracking gas absorption tower middle part or under Portion enters in tower, is contacted with the solvent to get off at the top of cracking gas absorption tower, and ethylene-rich gas is obtained by top of tower.
- 17. the method according to claim 16 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the cracking aspiration It is heavy aromatics to receive the solvent to get off at the top of tower.
- 18. the method according to claim 16 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the cracking qi leel Also include depropanizing tower from unit, the material of cracking gas absorb the bottom of the tower is sent into depropanizing tower, is obtained by the tower top of depropanizing tower The component of carbon three.
- 19. the method according to claim 18 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the component of carbon three It is sent into alkynes reaction unit and removes alkynes therein, propylene and propane is isolated from the material after removing alkynes.
- 20. the method according to claim 19 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the propane cycles In cracker into step (1).
- 21. the method according to claim 18 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that by the depropanization Tower also isolates drippolene, and the drippolene is partly or entirely fed through cracking gas absorption tower, and by cracking aspiration The middle part or middle and upper part of tower enter in cracking gas absorption tower.
- 22. the method according to claim 21 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the cracking qi leel Also include deheptanizer from unit, separating the part drippolene obtained by the depropanizing tower delivers to the deheptanizer, by The tower top of deheptanizer obtains drippolene, obtains heavy aromatics component by the bottom of towe of deheptanizer, the heavy aromatics component is sent into The top on cracking gas absorption tower.
- 23. the method according to claim 18 that ethylbenzene is prepared using low-carbon alkanes, it is characterised in that the cracking qi leel Also including debutanizing tower from unit, the component of carbon four is also isolated by the depropanizing tower, the component of carbon four is sent into debutanizing tower, The component of carbon four rich in butadiene is obtained by the tower top separation of debutanizing tower, drippolene is obtained by the bottom of towe of debutanizing tower.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110218140A (en) * | 2019-06-28 | 2019-09-10 | 常州瑞凯化工装备有限公司 | A kind of method of light hydrocarbon cracking production high-quality ethylbenzene |
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Address after: Room 801, Building 6, Greenbelt Central Plaza, North District of Changping Future Science and Technology City, Beijing 102209 Applicant after: Beijing and South Petrochemical Technology Co. Ltd. Applicant after: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Applicant after: Shenyang branch of CNPC Northeast Refining and Chemical Engineering Co., Ltd. Address before: Room 801, Building 6, Greenbelt Central Plaza, North District of Changping Future Science and Technology City, Beijing 102209 Applicant before: Beijing and South Petrochemical Technology Co. Ltd. Applicant before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Applicant before: Shenyang branch of CNPC Northeast Refining and Chemical Engineering Co., Ltd. |
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