CN107304157A - It is a kind of to be hydrogenated with the combination unit and method that iso-butane is produced with isomerization - Google Patents
It is a kind of to be hydrogenated with the combination unit and method that iso-butane is produced with isomerization Download PDFInfo
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- CN107304157A CN107304157A CN201610258430.2A CN201610258430A CN107304157A CN 107304157 A CN107304157 A CN 107304157A CN 201610258430 A CN201610258430 A CN 201610258430A CN 107304157 A CN107304157 A CN 107304157A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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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
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention relates to a kind of combination unit and method being hydrogenated with isomerization production iso-butane, the combination unit includes：One-stage hydrogenation reactor, one-stage hydrogenation separator, one-stage hydrogenation circulating pump, one section of recirculation cooler, hydrogenation input and output material heat exchanger, second-stage hydrogenation reactor, secondary hydrogenation feed heater, secondary hydrogenation separator, lightness-removing column, iso-butane finishing column, isomerization input and output material heat exchanger, isomerization feed heater, isomerization reactor.Methods described includes：The raw material of carbon four enters the combination unit via the feeding line of carbon four, and iso-butane and normal butane are made after hydrogenated, separation, and iso-butane is made after isomerization reaction, separation in wherein normal butane.The present invention can handle all rich in the lighter hydrocarbons of carbon four, while by waste heat recovery, improving the economic benefit of device.
Description
Technical field
The present invention relates to the lighter hydrocarbons field of carbon four, furtherly, it is related to a kind of hydrogenation and isomerization production
The combination unit and method of iso-butane.
Background technology
With deepening continuously for petrochemical industry working depth, liquefied gas, associated gas, oil refining are filled
Put and ethylene unit by-product C4Reasonable utilize of each component is increasingly subject to pay attention in cut.C4In cut
The 1,3-butadiene contained can be separated with the method for extracting rectifying as production synthetic rubber, C4Evaporate
Isobutene in point generates MTBE by ether-based device and methanol reaction and can be by further accurate
Fractionation obtains the 1- butylene of high-purity, and the utilization of other components of carbon four is also less.Iso-butane can be produced
Methyl methacrylate, isobutene, isobutanol, expoxy propane etc..In recent years due to isobutene, different
The demand such as butanol and expoxy propane increases year by year so that the utilization of iso-butane increasingly causes people's
Pay attention to, and because the alkyl plant that domestic oil product upgrading drives is expanded on a large scale, it is different in refinery C four
Butane will switch to balance by surplus rapidly, even (be likely to) not enough.Meanwhile, with shale gas association
Amount of butane continue to increase, because its contain a large amount of normal butanes, by the normal butane caused in refinery C four more
Difficulty seeks one's fortune, and added value is by continuous decrease.
The wide material sources of refinery C four, are broadly divided into two types, a kind of is olefin-containing≤5wt% saturated carbon
Four, another is that carbon four is main after 40~50wt% of olefin(e) centent unsaturated carbon four, ethylene unit ether
It is alkane and monoolefine, 30~60wt% of olefin(e) centent.Currently, these C 4 mixtures overwhelming majority
Burnt up as liquefied gas as fuel, chemical utilization rate is relatively low, due to for the in great demand of iso-butane, and
Normal butane economic value is limited, and the yield for thereby how improving iso-butane is just most important.
Chinese patent literature CN102294203A discloses the carbon four in a kind of catalytic pyrolysis ethene
Secondary hydrogenation device and technique, by using two sections of selective hydrogenations, it is to avoid 1,3-butadiene depth adds
The problem of hydrogen causes reactor coking, reduction catalyst service life and plant running cycle, can be direct
Mixing carbon four is hydrogenated with, the utilization rate of raw material is improved.But for containing a small amount of or no diene
The C 4 mixture of hydrocarbon is without reference to specific separation method, also without reference to impurity such as organic sulfur nitrogen
Removal methods, more without reference to isomerization reaction etc..
Chinese patent literature CN102188985A disclose a kind of C-4-fraction selective hydrogenation catalyst and
Its preparation method, the catalyst can be by the alkynes selective hydrogenation in C-4-fraction, and butadiene is substantially not
Loss, catalyst has high activity, high selectivity and preparation method simple, the characteristics of being widely used.
But the invention is mainly the selective hydrogenation to alkynes in C-4-fraction, without single in alkane, alkene mixture
The method of hydrotreating of alkene, and the simply preparation of catalyst, without reference to separation method, also without reference to
The removal methods of the impurity such as organic sulfur nitrogen, also without reference to isomerization reaction etc..
Chinese patent literature CN201410444683.X and CN1170632A disclose normal butane isomery
Change prepares catalyst and the application of iso-butane, but mainly catalyst system and process operation parameter, no
It is related to flow exploitation, is less related to the hydrogenation separation of olefin-containing material.
Chinese patent literature CN200680015930.8 discloses normal butane to the isomerization side of iso-butane
Method, but positive iso-butane mixture separated by permoselective membrane, and non-traditional ripe rectifying
Separation method, technique is using relatively difficult to achieve.
The content of the invention
Largely had more than needed for the normal butane that solves low value in the prior art, and the iso-butane of high added value is not
Sufficient the problems such as, the invention provides a kind of combination unit and method for producing iso-butane.By that will be hydrogenated with,
Isomerization process is combined, the present invention can handle it is all be rich in the lighter hydrocarbons of carbon four, including liquefied gas,
The carbon fourth class after associated gas, refinery C four and ethylene unit ether, meanwhile, by using heat-exchange network
Optimisation technique, by waste heat recovery, improves the economic benefit of device.
An object of the present invention is to provide a kind of combination unit for being hydrogenated with and iso-butane being produced with isomerization,
The combination unit includes：One-stage hydrogenation reactor, one-stage hydrogenation separator, one-stage hydrogenation circulating pump,
One section of recirculation cooler, hydrogenation input and output material heat exchanger, second-stage hydrogenation reactor, secondary hydrogenation charging add
Hot device, secondary hydrogenation separator, lightness-removing column, iso-butane finishing column, the heat exchange of isomerization input and output material
Device, isomerization feed heater and isomerization reactor；Wherein,
The feeding line of carbon four connection one-stage hydrogenation reactor, one-stage hydrogenation separator, hydrogenation input and output material
Second-stage hydrogenation reactor top is connected after heat exchanger, secondary hydrogenation feed heater；
One-stage hydrogenation separator bottom connects one-stage hydrogenation circulating pump, and pump discharge point two-way connects all the way
Connect after one section of recirculation cooler and to merge with the feeding line of carbon four, subsequently into one-stage hydrogenation reactor；Separately
Connection is hydrogenated with input and output material heat exchanger all the way；
Connection secondary hydrogenation separation dress after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger
Put, secondary hydrogenation separator is separated after being sequentially connected compressor suction tank, compressor with one-stage hydrogenation
Bottom of device pipeline merges, then connection hydrogenation input and output material heat exchanger；
With carbon after isomerization reaction after secondary hydrogenation separator bottom connection lightness-removing column input and output material heat exchanger
Four discharging pipelines merge connection lightness-removing column；
Lightness-removing column bottom connection lightness-removing column input and output material heat exchanger after connect iso-butane finishing column, iso-butane into
Product tower side line connects isomerization reaction after being sequentially connected isomerization input and output material heat exchanger, isomerization heater
Device entrance；
Lightness-removing column is connected after isomerization reactor outlet connection isomerization input and output material heat exchanger.
The one-stage hydrogenation reactor head is provided with fresh hydrogen feeding line.
The hydrogenation input and output material heat exchanger can be directly connected to by pipeline at the top of second-stage hydrogenation reactor.
The one-stage hydrogenation separator preferably includes one-stage hydrogenation hot knock-out pot, one-stage hydrogenation aftercooler
With the cold knockout drum of one-stage hydrogenation；
One-stage hydrogenation reactor bottom is connected at the top of one-stage hydrogenation hot knock-out pot, one-stage hydrogenation hot knock-out pot
It is sequentially connected at the top of one-stage hydrogenation aftercooler and the cold knockout drum of one-stage hydrogenation, the cold knockout drum of one-stage hydrogenation and connects
Connect compressor suction tank；The cold knockout drum bottom connection one-stage hydrogenation hot knock-out pot of one-stage hydrogenation；One section adds
Hydrogen hot knock-out pot bottom connects one-stage hydrogenation circulating pump.
The secondary hydrogenation separator is that secondary hydrogenation separator can in order to separate hydrogen and lighter hydrocarbons
Using one of following two compositions：
A) the secondary hydrogenation separator include secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and
The cold knockout drum of secondary hydrogenation；
Secondary hydrogenation thermal release is connected after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger
Secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation are sequentially connected at the top of tank, secondary hydrogenation hot knock-out pot,
Connection compressor suction tank at the top of the cold knockout drum of secondary hydrogenation；The cold knockout drum bottom connection two of secondary hydrogenation
Section hydrogenation hot knock-out pot；Secondary hydrogenation hot knock-out pot bottom connects lightness-removing column.
B) the secondary hydrogenation separator may also comprise secondary hydrogenation aftercooler and secondary hydrogenation separation
Tank；
It is sequentially connected after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger cold after secondary hydrogenation
Connection compressor suction tank, secondary hydrogenation at the top of device and secondary hydrogenation knockout drum, secondary hydrogenation knockout drum
Knockout drum bottom connects lightness-removing column.
According to two kinds of hydrogenation separators, can have after the hydrogenated input and output material heat exchanger heat exchange of reaction discharging
Two ways, one kind carries out gas-liquid separation to be introduced into secondary hydrogenation hot knock-out pot, and top gas phase passes through
Enter after the cooling of secondary hydrogenation aftercooler and connect at the top of the cold knockout drum of secondary hydrogenation, the cold knockout drum of secondary hydrogenation
Connect compressor suction tank, bottom connection secondary hydrogenation hot knock-out pot, secondary hydrogenation hot knock-out pot bottom liquid
Be connected lightness-removing column (as shown in Figure 1)；Another way is laggard first to be cooled down through secondary hydrogenation aftercooler
Enter secondary hydrogenation knockout drum and pass through gas-liquid separation, top gas phase connection compressor suction tank, bottom liquid phases
Connect lightness-removing column (as shown in Figure 2).
It is preferred to use first way.
Secondary hydrogenation feed heater described above can use common firing equipment in the prior art, such as：
Electric heater, steam heater or heating furnace.
Following technical scheme can specifically be used：
The combination unit of the production iso-butane includes：One-stage hydrogenation reactor, one-stage hydrogenation separation dress
Put, one-stage hydrogenation circulating pump, one section of recirculation cooler, hydrogenation input and output material heat exchanger, secondary hydrogenation it is anti-
Answer device, secondary hydrogenation feed heater, secondary hydrogenation separator, lightness-removing column, iso-butane finishing column,
Isomerization input and output material heat exchanger, isomerization feed heater and isomerization reactor；Wherein,
The feeding line of carbon four connection one-stage hydrogenation reactor, one-stage hydrogenation separator, hydrogenation input and output material
Second-stage hydrogenation reactor top is connected after heat exchanger, secondary hydrogenation feed heater；
One-stage hydrogenation separator bottom connects one-stage hydrogenation circulating pump, and pump discharge point two-way connects all the way
Connect after one section of recirculation cooler and to merge with the feeding line of carbon four, subsequently into one-stage hydrogenation reactor；Separately
Connection is hydrogenated with input and output material heat exchanger all the way；
Secondary hydrogenation thermal release is connected after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger
Tank；Secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation are sequentially connected at the top of secondary hydrogenation hot knock-out pot,
Separated after being sequentially connected compressor suction tank, compressor at the top of the cold knockout drum of secondary hydrogenation with one-stage hydrogenation
Bottom of device pipeline merges, then connection hydrogenation input and output material heat exchanger；The cold knockout drum bottom of secondary hydrogenation
Connect secondary hydrogenation hot knock-out pot；
With carbon after isomerization reaction after secondary hydrogenation hot knock-out pot bottom connection lightness-removing column input and output material heat exchanger
Four discharging pipelines merge connection lightness-removing column；
Lightness-removing column bottom connection lightness-removing column input and output material heat exchanger after connect iso-butane finishing column, iso-butane into
Product tower side line connects isomerization reaction after being sequentially connected isomerization input and output material heat exchanger, isomerization heater
Device entrance；
Lightness-removing column is connected after isomerization reactor outlet connection isomerization input and output material heat exchanger.
The second object of the present invention is to provide a kind of method using the combination unit production iso-butane,
Methods described includes：
The raw material of carbon four enters the combination unit via the feeding line of carbon four, is made after hydrogenated, separation
Iso-butane is made after isomerization reaction, separation in iso-butane and normal butane, wherein normal butane.
Specifically it may include following steps：
(a) by the raw material of carbon four out-of-bounds come enters one-stage hydrogenation reactor, by whole alkadienes and on a small quantity
Monoolefin hydrogenation saturation；
(b) one-stage hydrogenation reactor bottom material enters one-stage hydrogenation separator, isolates hydrogen and enters
Enter compressor suction tank, one-stage hydrogenation separator bottoms material is divided to two after entering one-stage hydrogenation circulating pump
Stock, is mixed into one-stage hydrogenation reactor, separately after one section of stock-traders' know-how recirculation cooler cooling with the charging of carbon four
Remaining monoolefin hydrogenation is satisfied into second-stage hydrogenation reactor after one hydrogenated input and output material heat exchanger heat exchange
With simultaneously imurity-removal；The impurity includes micro organic sulfur nitrogen, can be converted into H2S and NH3；
(c) into secondary hydrogenation point after the hydrogenated turnover glassware heat exchange of second-stage hydrogenation reactor bottom discharge
From device, the hydrogen isolated returns to second-stage hydrogenation reactor, secondary hydrogenation separator bottoms material
After being exchanged heat through lightness-removing column input and output material heat exchanger lightness-removing column is combined into carbon after isomerization reaction four；
(d) iso-butane finished product is entered after lightness-removing column bottoms material exchanges heat through lightness-removing column input and output material heat exchanger
Tower；Iso-butane product is obtained by top of tower by rectifying separation, tower reactor obtains light dydrocarbon heavy constituent, tower side
Mixture of the line extraction comprising normal butane and iso-butane；
(e) mixture comprising normal butane and iso-butane is through isomerization input and output material heat exchanger, isomery
Enter isomerization reactor after changing heater heat exchange, carry out isomerization reaction, normal butane is converted into different
Butane；
(f) isomerization reactor bottom discharge is separated after being exchanged heat through isomerization input and output material heat exchanger with hydrogenation
Bottom of device material is merged into lightness-removing column.
In step (a), the raw material of carbon four is mixed with hydrogenation recycle stock to entering one section after 30~160 DEG C
Hydrogenation reactor.The hydrogenation recycle stock is to enter one of two strands separated after one-stage hydrogenation circulating pump.
Present invention additionally comprises fresh hydrogen is passed through into one-stage hydrogenation reactor, it is passed through each during fresh hydrogen
The mixture of material also needs to meet said temperature requirement.
In step (b), one-stage hydrogenation separator bottoms material enters after being heated to 160~300 DEG C
Second-stage hydrogenation reactor.When secondary hydrogenation reaction temperature rising is very high, then two sections are not needed to add during normal production
Hydrogen feed heater heats up, and can reach reaction temperature by input and output material heat exchange, two are needed when only driving
Section hydrogenation feed heater, now, the material of hydrogenated input and output material heat exchanger heat exchange can be straight by pipeline
Tap into second-stage hydrogenation reactor.When secondary hydrogenation reaction temperature rising is not high, then removes and pass through during normal production
Input and output material heat exchange is outer, in addition it is also necessary to which secondary hydrogenation feed heater is heated.
In step (c), when secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation
When aftercooler and the cold knockout drum of secondary hydrogenation, the hydrogenated input and output material of second-stage hydrogenation reactor bottom discharge is changed
Hot device, which is cooled to after 50~100 DEG C, enters secondary hydrogenation hot knock-out pot, gas at the top of secondary hydrogenation hot knock-out pot
Enter the cold knockout drum of secondary hydrogenation after secondary hydrogenation aftercooler is cooled to 20~50 DEG C.
In step (c), when secondary hydrogenation separator includes secondary hydrogenation aftercooler and secondary hydrogenation point
During from tank, after the hydrogenated input and output material heat exchanger heat exchange of second-stage hydrogenation reactor bottoms material, then through two sections
Hydrogenation aftercooler, which is cooled to after 20~50 DEG C, enters secondary hydrogenation knockout drum.
Specifically, following technical scheme can be used：
(a) by the raw material of carbon four out-of-bounds come is mixed to 30~160 DEG C with hydrogenation recycle stock, fresh hydrogen
Enter one-stage hydrogenation reactor afterwards, by whole alkadienes and a small amount of monoolefin hydrogenation saturation；
(b) one-stage hydrogenation reactor bottom material enters one-stage hydrogenation separator, isolates hydrogen and enters
Enter compressor suction tank, one-stage hydrogenation separator bottoms material is divided to two after entering one-stage hydrogenation circulating pump
Stock, feeds, fresh hydrogen is mixed into one-stage hydrogenation after one section of stock-traders' know-how recirculation cooler cooling with carbon four
Reactor, another strand enters hydrogenation input and output material heat exchanger, then is warming up to through secondary hydrogenation feed heater
160~300 DEG C, second-stage hydrogenation reactor is finally entered by remaining monoolefin hydrogenation saturation and is had micro
Machine sulphur nitrogen is converted into H2S and NH3；
(c) second-stage hydrogenation reactor bottom discharge after hydrogenation charging heat exchange through with being cooled to 50~100 DEG C
After can have a two ways, one kind enter after being first cooled to 20~50 DEG C through secondary hydrogenation aftercooler two sections plus
Hydrogen knockout drum carries out gas-liquid separation, and top gas phase connection compressor suction tank, bottom liquid phases connection is de- light
Tower；Another way carries out gas-liquid separation to be introduced into secondary hydrogenation hot knock-out pot, and top gas phase passes through
Secondary hydrogenation aftercooler, which is cooled to after 20~50 DEG C, enters the cold knockout drum of secondary hydrogenation, cold point of secondary hydrogenation
Compressor suction tank, bottom connection secondary hydrogenation hot knock-out pot, secondary hydrogenation heat point are connected from tank top
Enter lightness-removing column from pot bottom liquid phase；
Secondary hydrogenation knockout drum or the cold knockout drum top gas phase of secondary hydrogenation are returned mostly as circulating hydrogen
Secondary hydrogenation reaction feed is returned, and maintains non-hydrogen gas content in circulation hydrogen system steady by pipeline of releasing
It is fixed；
(d) fresh hydrogen is from being out-of-bounds divided to two strands, and one is directly mixed into one-stage hydrogenation with the charging of carbon four
Reactor, another stock is combined into compressor with compressor suction head space gas body, after being pressurized through compressor
Enter hydrogenation input and output material heat exchanger together with one-stage hydrogenation separator bottoms material；
(e) with isomery after secondary hydrogenation hot knock-out pot bottoms material exchanges heat through lightness-removing column input and output material heat exchanger
Change carbon four after reaction and be mixed into lightness-removing column, separated by rectifying, top gaseous phase removing H2S, NH3
Deng fixed gas, liquid phase removing carbon two, the third light component of carbon, bottoms material enters iso-butane finishing column,
Separated by rectifying, iso-butane product is obtained at the top of iso-butane finishing column, tower reactor obtains light dydrocarbon restructuring
Point；
(f) by mixture of the iso-butane finishing column side take-off comprising normal butane and iso-butane with it is out-of-bounds new
The mixing of fresh hydrogen, 100 are heated to by isomerization input and output material heat exchanger, isomerization feed heater~
Enter isomerization reactor after 250 DEG C, normal butane is converted into iso-butane herein；
(g) material enters de- light through isomerization input and output material heat exchanger heat exchange Posterior circle after isomerization reaction
Tower, is separated by rectifying, removed overhead hydrogen, carbon two, the third light component of carbon, and tower reactor obtains just different
Butane mixture.
The present invention uses hydrogenation catalyst for nickel system or palladium series hydrocatalyst；Isomerization catalyst is
The catalyst that one or both of Pt, Pd, Ir are constituted.
The process conditions of each equipment of the present invention can use the process conditions generally used in the prior art,
In the present invention, preferably using following process conditions：
One-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 30~160 DEG C, pressure
For 1.5~4.5MPaG (gauge pressure, as follows), reaction temperature rising is 5~100 DEG C, and hydrogen/oil mol ratio is
0.05~10, liquid volume air speed is 0.5~10h-1；
Second-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 160~300 DEG C, pressure
Power is 1.5~4.5MPaG, and reaction temperature rising is 5~100 DEG C, and hydrogen/oil mol ratio is 0.2~5, liquid bulk
Product air speed is 0.5~6h-1；
The operating condition of lightness-removing column includes：Pressure is 1~3MPaG, and tower top operation temperature is 30~90 DEG C,
The number of plates is 30~120, and reflux ratio is 1~15；
The operating condition of iso-butane finishing column includes：Pressure is 0.1~1MPaG, and tower top operation temperature is
20~70 DEG C, the number of plates is 80~150, and reflux ratio is 1~20；
Isomerization reactor is fixed bed reactors, and reactor inlet temperature is 100~250 DEG C, pressure
For 1.0~4.0MPaG, reaction temperature rising is 5~50 DEG C, and liquid volume air speed is 1~20h-1。
It is characteristic of the invention that：
1) unsaturated olefin (including alkadienes and monoolefine) is completely converted into saturated hydrocarbons by being hydrogenated with,
The impurity such as organic sulfur nitrogen in raw material is converted into H2S and NH3Removed, it is to avoid to the shadow of product
Ring；
2) by rationally setting heat exchange order, recover energy to the full extent, reduce system energy consumption, carry
The high economic benefit of device, passes through a series of heat exchange network optimizations, saves energy consumption more than 15%；
3) bottom temperature is made to be below 150 DEG C by suitable operating parameter, 45 DEG C or so of tower top temperature,
It can be exchanged heat using more cheap low-pressure steam and recirculated cooling water, the steaming high-grade without outside intervention
The chilled water of vapour and high-quality；
4) present invention can handle all rich in carbon four by the way that hydrogenation and isomerization process are combined
Lighter hydrocarbons be used to produce iso-butane, especially the C4 materials containing a small amount of alkadienes and can also handle.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
It is of the invention by the way that exemplary embodiment of the invention is described in more detail with reference to accompanying drawing
Above-mentioned and other purposes, feature and advantage will be apparent, wherein, it is exemplary in the present invention
In embodiment, identical reference number typically represents same parts.
Fig. 1 is the combination unit schematic diagram of the production iso-butane of the present invention, and wherein secondary hydrogenation, which is separated, fills
Put including secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation.
Fig. 2 is the combination unit schematic diagram of the production iso-butane of the present invention, and wherein secondary hydrogenation, which is separated, fills
Put including secondary hydrogenation aftercooler and secondary hydrogenation knockout drum.
Description of reference numerals：
Second-stage hydrogenation reactor 1, hydrogenation input and output material heat exchanger 2, secondary hydrogenation feed heater 3, two
Section hydrogenation aftercooler 4, secondary hydrogenation knockout drum 5, secondary hydrogenation hot knock-out pot 6, cold point of secondary hydrogenation
From tank 7, compressor suction tank 8, compressor 9, lightness-removing column input and output material heat exchanger 10, lightness-removing column 11；
Condenser of light component removal column 12, lightness-removing column reboiler 13, iso-butane finishing column 14, the condensation of iso-butane finishing column
Device 15, iso-butane finishing column reboiler 16, isomerization input and output material heat exchanger 17, isomerization charging heating
Device 18, isomerization reactor 19, the raw material 20 of carbon four, periodic off-gases 21, one-stage hydrogenation hydrogen make-up 22,
Lightness-removing column top fixed gas 23, C2/C3Liquid phase 24, iso-butane product 25, light dydrocarbon heavy constituent 26, isomery
Change hydrogen make-up 27, one-stage hydrogenation reactor 28, one-stage hydrogenation aftercooler 29, one-stage hydrogenation thermal release
The cold knockout drum 31 of tank 30, one-stage hydrogenation, one-stage hydrogenation circulating pump 32, one section of recirculation cooler 33,
Secondary hydrogenation hydrogen make-up 34.
Embodiment
The preferred embodiment of the present invention is more fully described below with reference to accompanying drawings.
Iso-butane is produced using combination unit as shown in Figure 1.The combination unit includes：One-stage hydrogenation
Reactor 28, one-stage hydrogenation separator, one-stage hydrogenation circulating pump 32, one section of recirculation cooler 33,
Second-stage hydrogenation reactor 1, hydrogenation input and output material heat exchanger 2, secondary hydrogenation feed heater 3, two sections plus
Hydrogen separator, lightness-removing column 11, iso-butane finishing column 14, isomerization input and output material heat exchanger 17, isomery
Change feed heater 18 and isomerization reactor 19；Wherein,
The feeding line of carbon four connection one-stage hydrogenation reactor 28, one-stage hydrogenation separator, hydrogenation turnover
Expect connection second-stage hydrogenation reactor 1 top after heat exchanger 2, secondary hydrogenation feed heater 3；
One-stage hydrogenation separator bottom connection one-stage hydrogenation circulating pump 32, pump discharge point two-way, all the way
Merge after one section of recirculation cooler 33 of connection with the feeding line of carbon four, subsequently into one-stage hydrogenation reactor
28；Another road connection hydrogenation input and output material heat exchanger 2；
Connection secondary hydrogenation heat point after the bottom of second-stage hydrogenation reactor 1 connection hydrogenation input and output material heat exchanger 2
From tank 6；The top of secondary hydrogenation hot knock-out pot 6 is sequentially connected secondary hydrogenation aftercooler 4 and secondary hydrogenation is cold
Knockout drum 7, the cold top of knockout drum 7 of secondary hydrogenation is sequentially connected after compressor suction tank 8, compressor 9
Merge with one-stage hydrogenation separator bottom line, then connection hydrogenation input and output material heat exchanger 2；Two sections add
The hydrogen-cooled bottom of knockout drum 7 connection secondary hydrogenation hot knock-out pot 6；
With isomerization reaction after the bottom of secondary hydrogenation hot knock-out pot 6 connection lightness-removing column input and output material heat exchanger 10
The discharging of carbon four pipeline merges connection lightness-removing column 11 afterwards；
Connection iso-butane finishing column 14 after the bottom of lightness-removing column 11 connection lightness-removing column input and output material heat exchanger 10,
The side line of iso-butane finishing column 14 is sequentially connected isomerization input and output material heat exchanger 17, isomerization heater 18
The entrance of isomerization reactor 19 is connected afterwards；
Lightness-removing column 11 is connected after the outlet of isomerization reactor 19 connection isomerization input and output material heat exchanger 17；
The top of one-stage hydrogenation reactor 28 is provided with fresh hydrogen feeding line.
The method of production iso-butane includes：
(a) by the raw material 20 of carbon four and one-stage hydrogenation recycle stock, one-stage hydrogenation supplement hydrogen that out-of-bounds come
Gas 22 is mixed to one-stage hydrogenation reactor 28 is entered after 45 DEG C, by whole alkadienes and a small amount of monoolefine
It is hydrogenated with saturation；
(b) bottoms material of one-stage hydrogenation reactor 28 enters one-stage hydrogenation separator, isolates hydrogen
Gas enters compressor suction tank 8, and one-stage hydrogenation separator bottoms material enters one-stage hydrogenation circulating pump
It is divided to two strands after 32, one section is mixed into the charging of carbon four 20 after one section of a stock-traders' know-how recirculation cooler 33 cooling
Hydrogenation reactor 28, another strand enters hydrogenation input and output material heat exchanger 2, then feeds heating through secondary hydrogenation
Device 3 is warming up to 240 DEG C, finally enters second-stage hydrogenation reactor 1 by remaining monoolefin hydrogenation saturation and handle
Micro organic sulfur nitrogen is converted into H2S and NH3；
(c) bottom discharge of second-stage hydrogenation reactor 1 after hydrogenation charging heat exchange through with being cooled to after 80 DEG C first
Gas-liquid separation is carried out into secondary hydrogenation hot knock-out pot 6, top gas phase passes through secondary hydrogenation aftercooler 4
It is cooled to after 40 DEG C and enters the cold knockout drum 7 of secondary hydrogenation, the cold top of the knockout drum 7 connection pressure of secondary hydrogenation
Contracting machine suction tank 8, bottom connection secondary hydrogenation hot knock-out pot 6, the bottom liquid of secondary hydrogenation hot knock-out pot 6
Mutually enter lightness-removing column 11；
The cold top gas phase of knockout drum 7 of secondary hydrogenation returns to hydrogenation reaction charging mostly as circulating hydrogen,
And non-hydrogen gas stable content in the maintenance circulation hydrogen system of periodic off-gases 21 is discharged by pipeline of releasing.
(d) fresh hydrogen is from being out-of-bounds divided to two strands, and one is directly mixed into one-stage hydrogenation with the charging of carbon four
Reactor 28, another stock as secondary hydrogenation hydrogen make-up 34 from out-of-bounds with the top gas of compressor suction tank 8
Body is combined into compressor 9, after being pressurized through compressor 9 together with one-stage hydrogenation separator bottoms material
Into hydrogenation input and output material heat exchanger 2；
(e) bottoms material of secondary hydrogenation hot knock-out pot 6 exchanges heat by lightness-removing column input and output material heat exchanger 10
Lightness-removing column 11 is mixed into carbon after isomerization reaction four afterwards, is separated by rectifying, top gaseous phase removing
H2S, NH3Deng fixed gas, liquid phase removing carbon two, the third light component of carbon, bottoms material enters iso-butane
Finishing column 14, iso-butane product 25, tower are obtained by rectifying separation by the top of iso-butane finishing column 14
Kettle obtains light dydrocarbon heavy constituent 26；
(f) by mixture of the side take-off of iso-butane finishing column 14 comprising normal butane and iso-butane and out-of-bounds
Fresh hydrogen is that isomerization hydrogen make-up 27 is mixed, by isomerization input and output material heat exchanger 17, isomerization
Feed heater 18 is heated to after 160 DEG C entering isomerization reactor 19, is herein converted into normal butane
Iso-butane；
(g) material enters de- through the heat exchange Posterior circle of isomerization input and output material heat exchanger 17 after isomerization reaction
Light tower 11, is separated, removed overhead hydrogen, carbon two, the third light component of carbon, tower reactor are obtained by rectifying
Positive iso-butane mixture.
Using following process conditions：
One-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 45 DEG C, and pressure is
3.6MPaG, reaction temperature rising is 20 DEG C, and hydrogen/oil mol ratio is 0.1, and liquid volume air speed is 2.5h-1；
Second-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 240 DEG C, and pressure is
3MPaG, reaction temperature rising is 25 DEG C, and hydrogen/oil mol ratio is 1.1, and liquid volume air speed is 2.0h-1；
The operating condition of lightness-removing column includes：Pressure is 1.8MPaG, and tower top operation temperature is 50 DEG C, tower
Plate number is 80, and reflux ratio is 10；
The operating condition of iso-butane finishing column includes：Pressure is 0.5MPaG, and tower top operation temperature is
45 DEG C, the number of plates is 130, and reflux ratio is 6；
Isomerization reactor is fixed bed reactors, and reactor inlet temperature is 160 DEG C, and pressure is
3.3MPaG, reaction temperature rising is 30 DEG C, and liquid volume air speed is 10h-1。
Using system as shown in Figure 1, the result of table 1 is obtained.
As a result show, using the system and method iso-butane of the present invention, iso-butane yield ＞ 97%.
Table 1
By said apparatus and process, energy consumption more than 15% is saved.
It is described above various embodiments of the present invention, described above is exemplary, and exhaustive
Property, and it is also not necessarily limited to disclosed each embodiment.In the model without departing from illustrated each embodiment
Enclose and spirit in the case of, many modifications and changes for those skilled in the art
It will be apparent from.
Claims (10)
1. a kind of be hydrogenated with the combination unit that iso-butane is produced with isomerization, it is characterised in that：
The combination unit includes：One-stage hydrogenation reactor, one-stage hydrogenation separator, one-stage hydrogenation are followed
Ring pump, one section of recirculation cooler, hydrogenation input and output material heat exchanger, second-stage hydrogenation reactor, secondary hydrogenation
Feed heater, secondary hydrogenation separator, lightness-removing column, iso-butane finishing column, isomerization input and output material
Heat exchanger, isomerization feed heater and isomerization reactor；Wherein,
The feeding line of carbon four connection one-stage hydrogenation reactor, one-stage hydrogenation separator, hydrogenation input and output material
Second-stage hydrogenation reactor top is connected after heat exchanger, secondary hydrogenation feed heater；
One-stage hydrogenation separator bottom connects one-stage hydrogenation circulating pump, and pump discharge point two-way connects all the way
Connect after one section of recirculation cooler and to merge with the feeding line of carbon four, subsequently into one-stage hydrogenation reactor；Separately
Connection is hydrogenated with input and output material heat exchanger all the way；
Connection secondary hydrogenation separation dress after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger
Put, secondary hydrogenation separator is separated after being sequentially connected compressor suction tank, compressor with one-stage hydrogenation
Bottom of device pipeline merges, then connection hydrogenation input and output material heat exchanger；
With carbon after isomerization reaction after secondary hydrogenation separator bottom connection lightness-removing column input and output material heat exchanger
Four discharging pipelines merge connection lightness-removing column；
Lightness-removing column bottom connection lightness-removing column input and output material heat exchanger after connect iso-butane finishing column, iso-butane into
Product tower side line connects isomerization reaction after being sequentially connected isomerization input and output material heat exchanger, isomerization heater
Device entrance；
Lightness-removing column is connected after isomerization reactor outlet connection isomerization input and output material heat exchanger.
2. hydrogenation as claimed in claim 1 and isomerization produce the combination unit of iso-butane, its feature
It is：
The one-stage hydrogenation separator includes one-stage hydrogenation hot knock-out pot, one-stage hydrogenation aftercooler and one
The cold knockout drum of section hydrogenation；
One-stage hydrogenation reactor bottom is connected at the top of one-stage hydrogenation hot knock-out pot, one-stage hydrogenation hot knock-out pot
It is sequentially connected at the top of one-stage hydrogenation aftercooler and the cold knockout drum of one-stage hydrogenation, the cold knockout drum of one-stage hydrogenation and connects
Connect compressor suction tank；The cold knockout drum bottom connection one-stage hydrogenation hot knock-out pot of one-stage hydrogenation；One section adds
Hydrogen hot knock-out pot bottom connects one-stage hydrogenation circulating pump.
3. hydrogenation as claimed in claim 1 and isomerization produce the combination unit of iso-butane, its feature
It is：
The secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and two
The cold knockout drum of section hydrogenation；
Secondary hydrogenation thermal release is connected after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger
Secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation are sequentially connected at the top of tank, secondary hydrogenation hot knock-out pot,
Connection compressor suction tank at the top of the cold knockout drum of secondary hydrogenation；The cold knockout drum bottom connection two of secondary hydrogenation
Section hydrogenation hot knock-out pot；Secondary hydrogenation hot knock-out pot bottom connects lightness-removing column.
4. hydrogenation as claimed in claim 1 and isomerization produce the combination unit of iso-butane, its feature
It is：
The secondary hydrogenation separator includes secondary hydrogenation aftercooler and secondary hydrogenation knockout drum；
It is sequentially connected after second-stage hydrogenation reactor bottom connection hydrogenation input and output material heat exchanger cold after secondary hydrogenation
Connection compressor suction tank, secondary hydrogenation at the top of device and secondary hydrogenation knockout drum, secondary hydrogenation knockout drum
Knockout drum bottom connects lightness-removing column.
5. a kind of combination unit production iso-butane using as described in any one in claim 1-4
Method, it is characterised in that methods described includes：
The raw material of carbon four enters the combination unit via the feeding line of carbon four, is made after hydrogenated, separation
Iso-butane is made after isomerization reaction, separation in iso-butane and normal butane, wherein normal butane.
6. the method for iso-butane is produced as claimed in claim 5, it is characterised in that methods described bag
Include：
(a) by the raw material of carbon four out-of-bounds come enters one-stage hydrogenation reactor, by whole alkadienes and on a small quantity
Monoolefin hydrogenation saturation；
(b) one-stage hydrogenation reactor bottom material enters one-stage hydrogenation separator, isolates hydrogen and enters
Enter compressor suction tank, one-stage hydrogenation separator bottoms material is divided to two after entering one-stage hydrogenation circulating pump
Stock, is mixed into one-stage hydrogenation reactor, separately after one section of stock-traders' know-how recirculation cooler cooling with the charging of carbon four
Remaining monoolefin hydrogenation is satisfied into second-stage hydrogenation reactor after one hydrogenated input and output material heat exchanger heat exchange
With simultaneously imurity-removal；
(c) into secondary hydrogenation point after the hydrogenated input and output material heat exchanger of second-stage hydrogenation reactor bottom discharge
From device, the hydrogen isolated returns to second-stage hydrogenation reactor, secondary hydrogenation separator bottoms material
After being exchanged heat through lightness-removing column input and output material heat exchanger lightness-removing column is combined into carbon after isomerization reaction four；
(d) iso-butane finished product is entered after lightness-removing column bottoms material exchanges heat through lightness-removing column input and output material heat exchanger
Tower；Iso-butane product is obtained by top of tower by rectifying separation, tower reactor obtains light dydrocarbon heavy constituent, tower side
Mixture of the line extraction comprising normal butane and iso-butane；
(e) mixture comprising normal butane and iso-butane is through isomerization input and output material heat exchanger, isomery
Enter isomerization reactor after changing heater heat exchange, carry out isomerization reaction, normal butane is converted into different
Butane；
(f) isomerization reactor bottom discharge is separated after being exchanged heat through isomerization input and output material heat exchanger with hydrogenation
Bottom of device material is merged into lightness-removing column.
7. the method for iso-butane is produced as claimed in claim 6, it is characterised in that：
In step (a), the raw material of carbon four is mixed with hydrogenation recycle stock to entering one section after 30~160 DEG C
Hydrogenation reactor；
In step (b), one-stage hydrogenation separator bottoms material enters after being heated to 160~300 DEG C
Second-stage hydrogenation reactor.
8. the method for iso-butane is produced as claimed in claim 6, it is characterised in that：
In step (c), when secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation
When aftercooler and the cold knockout drum of secondary hydrogenation, the hydrogenated input and output material of second-stage hydrogenation reactor bottom discharge is changed
Hot device, which is cooled to after 50~100 DEG C, enters secondary hydrogenation hot knock-out pot, gas at the top of secondary hydrogenation hot knock-out pot
Enter the cold knockout drum of secondary hydrogenation after secondary hydrogenation aftercooler is cooled to 20~50 DEG C.
9. the method for iso-butane is produced as claimed in claim 6, it is characterised in that：
In step (c), when secondary hydrogenation separator includes secondary hydrogenation aftercooler and secondary hydrogenation point
During from tank, after the hydrogenated input and output material heat exchanger heat exchange of second-stage hydrogenation reactor bottoms material, then through two sections
Hydrogenation aftercooler, which is cooled to after 20~50 DEG C, enters secondary hydrogenation knockout drum.
10. the method for the production iso-butane as described in any one in claim 6-9, it is characterised in that：
One-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 30~160 DEG C, pressure
For 1.5~4.5MPaG, reaction temperature rising is 5~100 DEG C, and hydrogen/oil mol ratio is 0.05~10, liquid bulk
Product air speed is 0.5~10h-1；
Second-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 160~300 DEG C, pressure
Power is 1.5~4.5MPaG, and reaction temperature rising is 5~100 DEG C, and hydrogen/oil mol ratio is 0.2~5, liquid bulk
Product air speed is 0.5~6h-1；
The operating condition of lightness-removing column includes：Pressure is 1~3MPaG, and tower top operation temperature is 30~90 DEG C,
The number of plates is 30~120, and reflux ratio is 1~15；
The operating condition of iso-butane finishing column includes：Pressure is 0.1~1MPaG, and tower top operation temperature is
20~70 DEG C, the number of plates is 80~150, and reflux ratio is 1~20；
Isomerization reactor is fixed bed reactors, and reactor inlet temperature is 100~250 DEG C, pressure
For 1.0~4.0MPaG, reaction temperature rising is 5~50 DEG C, and liquid volume air speed is 1~20h-1。
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