CN109265306A - A kind of carbon four adds four method of hydrotreating of process units and carbon of hydrogen - Google Patents
A kind of carbon four adds four method of hydrotreating of process units and carbon of hydrogen Download PDFInfo
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- CN109265306A CN109265306A CN201710581540.7A CN201710581540A CN109265306A CN 109265306 A CN109265306 A CN 109265306A CN 201710581540 A CN201710581540 A CN 201710581540A CN 109265306 A CN109265306 A CN 109265306A
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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
- C07C5/05—Partial hydrogenation
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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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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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
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Abstract
The invention discloses a kind of carbon four plus four method of hydrotreating of process units and carbon of hydrogen.Described device includes: debutanizing tower, one-stage hydrogenation reactor, one section of circulating cooling/heater, one-stage hydrogenation separator, second-stage hydrogenation reactor, secondary hydrogenation input and output material heat exchanger, secondary hydrogenation feed heater, debutanizing tower intermediate reboiler, secondary hydrogenation separator, compressor suction tank, circulating hydrogen compressor；Secondary hydrogenation separator includes: secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation；Or including secondary hydrogenation aftercooler and secondary hydrogenation knockout drum.The present invention can handle all carbon four, including low alkene carbon four, high alkene carbon four, richness alkynes and two olefinic carbons four etc. recycle waste heat rich in four lighter hydrocarbons of carbon, improve the economic benefit of device.
Description
Technical field
The present invention relates to four lighter hydrocarbons fields of carbon, furtherly, be related to a kind of carbon four plus hydrogen process units and carbon four plus
Hydrogen methods.
Background technique
With deepening continuously for petrochemical industry working depth, to liquefied gas, associated gas, oil refining apparatus and ethylene unit
Reasonable utilize of each component is paid more and more attention in the C 4 fraction of by-product.The 1,3- fourth two contained in cracking of ethylene by-product C 4 fraction
The isobutene that alkene can extract for producing synthetic rubber, in raffinate by butadiene extraction device can pass through ether-based device
It is reacted with methanol and generates MTBE, and the 1- butylene of high-purity can be obtained by further precision fractionation, but with domestic in recent years
MTBE production capacity increase severely, the especially a large amount of by-product MTBE of PO/MTBE device, the following MTBE supply and demand close to balance, and Countries and
MTBE is classified as pollutant and is forbidden to use by area, therefore the utilization of raffinate is problem to be solved.Fourth two simultaneously
Four alkynes of carbon of alkene extraction device by-product, general 20%wt of alkyne concentration or so, even up to 40%wt, these are rich in alkynes
Residual fraction fails to efficiently use, and because high concentration alkynes easily polymerize explosion, and there are safety problems, is generally carried out using raffinate
Dilution is burnt up after reducing alkyne concentration as fuel.It is used if being processed to be converted into valuable fraction, it will
Greatly improve ethylene unit comprehensive benefit.Refinery reforms, Atmospheric vacuum and a large amount of carbon four of devices by-product such as is hydrocracked.It is current these
The C4 mixture overwhelming majority is burnt up as liquefied gas as fuel, and chemical utilization rate is lower.And on the other hand as oil quality upgrades
With the popularization of state V petrol and diesel oil, alkylate oil demand can be more and more vigorous, while ethylene cracking material lighting trend, needs big
Amount saturation C4 alkane, so that C4 comprehensive utilization especially separation, hydrogenation technique route, more and more attract people's attention.
Refinery C four is from a wealth of sources, is broadly divided into two types, another one is olefin-containing≤5wt% saturated carbon four
Kind is the unsaturated carbon four of 40~50wt% of olefin(e) centent, and the raw material of alkyl plant is iso-butane, butylene, and normal butane is then lazy
Property component, and ethylene unit needs a large amount of alkane, especially normal butane as cracking stock after, yield of ethene is higher.
Chinese patent literature CN102294203A discloses four secondary hydrogenation of the carbon dress in a kind of catalytic pyrolysis ethylene
It sets and technique avoids 1,3-butadiene deep hydrogenation and reactor coking, reduction is caused to be urged by using two sections of selective hydrogenations
The problem of agent service life and the device cycle of operation, directly can carry out adding hydrogen, improve the utilization rate of raw material to mixing carbon four.
But for containing a small amount of or the C 4 mixture of alkadienes is not without reference to specific separation method, also without reference to organic sulfur
The removal methods of the impurity such as nitrogen more separate production alkylation carbon four etc. without reference to carbon four.
Chinese patent literature CN102188985A discloses a kind of C-4-fraction selective hydrogenation catalyst and preparation method thereof,
The catalyst can not lose the alkynes selective hydrogenation in C-4-fraction, butadiene substantially, and catalyst has high activity, Gao Xuan
Selecting property and preparation method is simple, is widely used.But the invention is mainly the selective hydrogenation to alkynes in C-4-fraction, is not had
The method of hydrotreating of monoolefine in alkane, alkene mixture, and the only preparation of catalyst, without reference to separation method, also without reference to
The removal methods of the impurity such as organic sulfur nitrogen more separate production alkylation carbon four etc. without reference to carbon four.
Chinese patent literature CN105566032 discloses the process for selective hydrogenation of rich alkynes carbon four, i.e., by Butadiene Extraction
Four alkynes of carbon of device by-product is separated through rectifying column first, is produced after the chosen property acetylene hydrogenation of tower top material, the invention is main
For be still alkynes selective hydrogenation, without reference to alkynes, alkadienes, monoolefine complete plus hydrogen and the separation of carbon four etc.
Deng.
Summary of the invention
To solve the problem of complex utilization such as four alkynes of carbon, refinery C four, butadiene raffinate of low value in the prior art,
The present invention provides a kind of carbon four plus the process units and method of hydrogen.By being separated, the works such as one-stage hydrogenation, secondary hydrogenation
Skill, the present invention can handle all materials rich in four alkynes of carbon or alkadienes and monoolefine, including liquefied gas, oil field association
Gas, refinery C four and ethylene unit carbon-4 etc., meanwhile, by using heat exchange network optimization technology, waste heat is recycled, is improved
The economic benefit of device.
An object of the present invention is to provide the process units of a kind of carbon four plus hydrogen, and described device includes: debutanizing tower, one
Section hydrogenator, one section of circulating cooling/heater, one-stage hydrogenation separator, second-stage hydrogenation reactor, secondary hydrogenation disengaging
Expect heat exchanger, secondary hydrogenation feed heater, debutanizing tower intermediate reboiler, secondary hydrogenation separator, compressor suction tank,
Circulating hydrogen compressor；Wherein,
Poor four feeding line of butylene carbon and rich four feeding line of butylene carbon are separately connected debutanizing tower upper and lower part；
Debutanizing tower bottom outlet connects one-stage hydrogenation reactor top after merging with rich four feeding line of alkynes carbon；
Hydrogen feed line connects one-stage hydrogenation reactor top；
One-stage hydrogenation reactor bottom connects one-stage hydrogenation separator, one-stage hydrogenation separation unit overhead connect compressor
Suction tank；
One-stage hydrogenation separator bottom outlet divides two-way, all the way connect one section of circulating cooling/heater after with richness
Alkynes carbon four merges, and then connects one-stage hydrogenation reactor；Another way is sequentially connected secondary hydrogenation input and output material after merging with recycle hydrogen
Second-stage hydrogenation reactor top is connected after heat exchanger, secondary hydrogenation feed heater；
Two are connected after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Section plus hydrogen separator；
Secondary hydrogenation separator is sequentially connected after compressor suction tank, circulating hydrogen compressor and the carbon from one-stage hydrogenation
Four feeding lines merge, and then connect secondary hydrogenation input and output material heat exchanger.
In accordance with the present invention it is preferred that circulating hydrogen compressor outlet line divides two-way, all the way with the carbon after one-stage hydrogenation
Four fraction lines connect secondary hydrogenation input and output material heat exchanger after merging, another way connects in the middle part of second-stage hydrogenation reactor.
According to an embodiment of the present invention, the one-stage hydrogenation separator includes one-stage hydrogenation hot knock-out pot, one section
Add hydrogen aftercooler and the cold knockout drum of one-stage hydrogenation；
Secondary hydrogenation separator be in order to separate hydrogen and carbon four, according to the present invention, the secondary hydrogenation separator
One of following two mode can be used:
A) the secondary hydrogenation separator includes that secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and secondary hydrogenation are cold
Knockout drum；
Two are connected after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Section heat from hydrogenation knockout drum, secondary hydrogenation hot knock-out pot top are sequentially connected secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation,
Connect compressor suction tank at the top of the cold knockout drum of secondary hydrogenation；The cold knockout drum bottom of secondary hydrogenation connects secondary hydrogenation thermal release
Tank；
B) the secondary hydrogenation separator includes adding two sections of hydrogen aftercoolers and secondary hydrogenation knockout drum；
Successively connect after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Connect secondary hydrogenation aftercooler and secondary hydrogenation knockout drum, connect compressor suction tank at the top of secondary hydrogenation knockout drum.
According to two kinds of secondary hydrogenation separators, reaction discharging can have two after the heat exchange of secondary hydrogenation input and output material heat exchanger
Kind mode, one kind carrying out gas-liquid separation to be introduced into secondary hydrogenation hot knock-out pot, and top gas phase is cold by secondary hydrogenation aftercooler
But enter the cold knockout drum of secondary hydrogenation afterwards, circulating hydrogen compressor suction tank, bottom connection are connected at the top of the cold knockout drum of secondary hydrogenation
Secondary hydrogenation hot knock-out pot, secondary hydrogenation hot knock-out pot bottom liquid phases produce (as shown in Figure 1)；Another way is first through two sections
Enter secondary hydrogenation knockout drum after adding hydrogen aftercooler cooling by gas-liquid separation, top gas phase connects circulating hydrogen compressor sucking
Tank, bottom liquid phases produce (as shown in Figure 2).
It is preferred that using the second way.
Common heating equipment in the prior art can be used in secondary hydrogenation feed heater described above, such as: electric heater,
Steam heater or heating furnace.
Following technical scheme specifically can be used:
The process units of a kind of carbon four plus hydrogen is provided, described device includes: debutanizing tower, one-stage hydrogenation reactor, one section
Circulating cooling/heater, one-stage hydrogenation separator, second-stage hydrogenation reactor, secondary hydrogenation input and output material heat exchanger, secondary hydrogenation
Feed heater, debutanizing tower intermediate reboiler, secondary hydrogenation separator, compressor suction tank, circulating hydrogen compressor.
Poor four feeding line of butylene carbon and rich four feeding line of butylene carbon are separately connected debutanizing tower upper and lower part；
Debutanizing tower bottom connects one-stage hydrogenation reactor top after merging with rich alkynes carbon four；
Hydrogen connects one-stage hydrogenation reactor top through hydrogen feed line；
One-stage hydrogenation reactor bottom connects one-stage hydrogenation separator, and one-stage hydrogenation separation unit overhead connects two sections and adds
The compressor suction tank of hydrogen；
Two-way is divided in one-stage hydrogenation separator bottom, closes after connecting one section of circulating cooling/heater all the way with rich alkynes carbon four
And then connect one-stage hydrogenation reactor；Another way merge with recycle hydrogen after connect secondary hydrogenation input and output material heat exchanger, two sections plus
Second-stage hydrogenation reactor top is connected after hydrogen feed heater；
Two are connected after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Section heat from hydrogenation knockout drum；It is sequentially connected at the top of secondary hydrogenation hot knock-out pot and adds hydrogen aftercooler and add hydrogen-cooled knockout drum, add hydrogen-cooled point
It is sequentially connected after compressor suction tank, circulating hydrogen compressor from tank top and divides two-way, evaporated all the way with the carbon four from one-stage hydrogenation
It is in charge of line merging, then connection plus hydrogen input and output material heat exchanger, another way connects in the middle part of second-stage hydrogenation reactor；Cold point of secondary hydrogenation
Secondary hydrogenation hot knock-out pot is connected from pot bottom.
The second object of the present invention is to provide a kind of four method of hydrotreating of carbon, which comprises
Poor butylene carbon four and rich butylene carbon four respectively enter debutanizing tower upper and lower part, and through separating, debutanization tower top is obtained
To not hydrogenating carbon four, kettle material obtains saturated carbon four after merging with rich alkynes carbon four after one-stage hydrogenation, secondary hydrogenation.Wherein not
Hydrogenating carbon four can be used as raw material for alkylation.
Specifically it can comprise the following steps that
(a) poor butylene carbon four and rich butylene respectively via poor four feeding line of butylene carbon and rich four feeding line of butylene carbon into
Enter debutanizing tower upper and lower part, through separating, debutanization tower top obtains not hydrogenating carbon four；
(b) debutanization kettle material, four, the one sections of cyclic carbons four of rich alkynes carbon out-of-bounds come and the fresh hydrogen out-of-bounds come enter
Alkynes, diene hydrogenation are monoolefine or saturated hydrocarbons by one-stage hydrogenation reactor reaction；
(c) discharging of one-stage hydrogenation reactor bottom enters one-stage hydrogenation separator, and the hydrogen isolated is sent to two sections and adds
The compressor suction tank of hydrogen, one-stage hydrogenation separator bottoms material are divided to two strands, one as recycle stock through one section circulation/it is cold
But one-stage hydrogenation reactor, another burst of charging as secondary hydrogenation reaction are returned to after heater heat exchange；
(d) as the C-4-fraction after the one-stage hydrogenation of secondary hydrogenation reaction feed, the circulation come with circulating hydrogen compressor
Hydrogen mixing enters second-stage hydrogenation reactor for olefins hydrogenation after secondary hydrogenation input and output material heat exchanger, two section feeding heaters
And imurity-removal, the impurity include micro organic sulfur nitrogen etc.；
(e) second-stage hydrogenation reactor bottom discharge enters secondary hydrogenation separation dress after secondary hydrogenation input and output material heat exchanger
It sets, the hydrogen isolated enters circulating hydrogen compressor, and secondary hydrogenation separator bottom obtains adding the saturated carbon four after hydrogen；
(f) through recycle hydrogen pressure after secondary hydrogenation separation unit overhead hydrogen merges with one-stage hydrogenation separation unit overhead hydrogen
The boosting of contracting machine is used as two sections of circulating hydrogens, and two sections of circulating hydrogens are divided into two strands, one and the C-4-fraction after one-stage hydrogenation
Two sections of input and output material heat exchangers are combined into, another strand enters in the middle part of second-stage hydrogenation reactor.
In step (d), the C-4-fraction after one-stage hydrogenation enters second-stage hydrogenation reactor after being heated to 100~300 DEG C.
When secondary hydrogenation reaction temperature rising is very high, then the heating of secondary hydrogenation feed heater is not needed during normal production, pass through two sections of disengaging
Material heat exchange can reach reaction temperature, secondary hydrogenation feed heater be needed when only driving, at this point, changing through secondary hydrogenation input and output material
The material of hot device heat exchange can be directly entered second-stage hydrogenation reactor by pipeline.When secondary hydrogenation reaction temperature rising is not high, then normally
When production in addition to being exchanged heat by input and output material, it is also necessary to which secondary hydrogenation feed heater is heated.
In step (e), when secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and two sections
When adding hydrogen-cooled knockout drum, the hydrogenated input and output material heat exchanger of second-stage hydrogenation reactor bottom discharge, debutanizing tower reboiler heat exchange drop
For temperature to secondary hydrogenation hot knock-out pot is entered after 50~100 DEG C, secondary hydrogenation hot knock-out pot top gas phase is cold after secondary hydrogenation
Device enters the cold knockout drum of secondary hydrogenation after being cooled to 20~50 DEG C.
In step (e), when secondary hydrogenation separator includes secondary hydrogenation aftercooler and secondary hydrogenation knockout drum, two sections
The hydrogenated input and output material heat exchanger of hydrogenator bottoms material, debutanizing tower reboiler heat exchange after, then through add secondary hydrogenation after it is cold
Device enters secondary hydrogenation knockout drum after being cooled to 20~50 DEG C.
Specifically, following technical scheme can be used:
(a) by out-of-bounds Lai the charging of poor butylene carbon four and rich butene feed respectively enter debutanizing tower upper and lower part, pass through
Rectifying separation, debutanization tower top obtain rich in iso-butane, butene-1, isobutene raw material for alkylation, tower reactor be rich in normal butane,
The C 4 materials of butene-2；
(b) debutanization kettle material, four, the one sections of cyclic carbons four of rich alkynes carbon out-of-bounds come and the fresh hydrogen out-of-bounds come merge
It reacts after into one-stage hydrogenation reactor top, is monoolefine and saturated hydrocarbons by alkynes, diene hydrogenation；
(c) discharging of one-stage hydrogenation reactor bottom enters one-stage hydrogenation separator, and the hydrogen isolated is sent to two sections and adds
The compressor suction tank of hydrogen, one-stage hydrogenation separator bottoms material are divided to two strands, one as recycle stock through one section circulation/it is cold
But heater exchanges heat to return one-stage hydrogenation reactor, another burst of charging as secondary hydrogenation reaction after 20~80 DEG C；
(d) C-4-fraction after one-stage hydrogenation, mixed with two sections of recycle hydrogens through secondary hydrogenation input and output material heat exchanger, two sections into
Material heater enters second-stage hydrogenation reactor and turns by olefins hydrogenation and micro organic sulfur nitrogen after being warming up to 100~300 DEG C
Turn to H2S and NH3；
(e) second-stage hydrogenation reactor bottom discharge is passed through exchanges heat with secondary hydrogenation input and output material heat exchanger, debutanizing tower reboiler
After be cooled to 50~100 DEG C after can be a kind of first to enter two after secondary hydrogenation aftercooler is cooled to 20~50 DEG C there are two types of mode
Section plus hydrogen knockout drum carry out gas-liquid separation, top gas phase connect compressor suction tank, and bottom is four product of saturated carbon；Another kind side
Formula is to be introduced into secondary hydrogenation hot knock-out pot to carry out gas-liquid separation, and top gas phase is cooled to 20~50 by secondary hydrogenation aftercooler
Enter the cold knockout drum of secondary hydrogenation, connect compressor suction tank at the top of the cold knockout drum of secondary hydrogenation after DEG C, bottom connects two sections and adds
Hydrogen hot knock-out pot, secondary hydrogenation hot knock-out pot bottom are four product of saturated carbon.
Secondary hydrogenation knockout drum or the cold knockout drum top gas phase of secondary hydrogenation return to two sections mostly as circulating hydrogen and add
Hydrogen reaction feed, and non-hydrogen gas stable content in circulation hydrogen system is maintained by pipeline of releasing
The process conditions of each equipment of the invention can be used the process conditions generallyd use in the prior art, in the present invention,
Preferably use following process conditions:
The operating condition of debutanizing tower includes: that pressure is 0.2~1.0MPaG, and tower top operation temperature is 20~80 DEG C, column plate
Number is 50~200, and reflux ratio is 1~20；
The one-stage hydrogenation reactor is trickle bed reactor, the preferably trickle bed reactor of upper entering and lower leaving, reactor
Inlet temperature is 20~80 DEG C, and pressure is 1.5~4.5MPaG, and reaction temperature rising is 5~100 DEG C, and hydrogen/oil mol ratio is 0.2~5,
Liquid volume air speed is 0.5~6h-1, catalyst is palladium system or nickel catalyst；
The second-stage hydrogenation reactor is fixed bed reactors, and reactor inlet temperature is 100~300 DEG C, pressure 1.5
~4.5MPaG, reaction temperature rising are 5~150 DEG C, and hydrogen/oil mol ratio is 0.2~5, and liquid volume air speed is 0.5~6h-1, catalyst
For palladium system or molybdenum nickel catalyst.
According to the present invention, the carbon four includes but is not limited to the liquefaction rich in four alkynes of carbon or alkadienes and monoolefine
Gas, associated gas, refinery C four or ethylene unit carbon-4.
The invention has the characteristics that
1) by isolated not hydrogenating carbon four of rectifying, residual carbon four carries out hydrotreating；Hydrogenating carbon four can not made directly
For raw material for alkylation；
2) alkadienes, alkynes are hydrogenated to by monoolefine and saturated hydrocarbons by one-stage hydrogenation, it will be unsaturated by secondary hydrogenation
Monoolefine is completely converted into saturated hydrocarbons, converts H for the impurity such as organic sulfur nitrogen in raw material2S and NH3It is removed, is avoided to production
The influence of product；
3) it by rationally setting heat exchange sequence, recovers energy to the full extent, reduces system energy consumption, improve the warp of device
Benefit of helping saves 15% or more energy consumption by a series of heat exchange network optimizations；
4) make debutanization bottom temperature lower than 100 DEG C, 45 DEG C of tower top temperature or so by suitable operating parameter, using compared with
Cheap low-pressure steam and recirculated cooling water can exchange heat, without the external chilled water for intervening high-grade steam and high-quality；
5) present invention can handle all carbon four, including low alkene carbon by the separation of carbon four, one-stage hydrogenation and secondary hydrogenation
Four, high alkene carbon four, rich alkynes and two olefinic carbons four etc..
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its
Its purpose, feature and advantage will be apparent, wherein in exemplary embodiment of the invention, identical reference label
Typically represent same parts.
Fig. 1 is the carbon four of one embodiment of the present invention plus the process units schematic diagram of hydrogen, and wherein secondary hydrogenation separation fills
It sets including secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation.
Fig. 2 is the carbon four of another embodiment of the present invention plus the process units schematic diagram of hydrogen, and wherein secondary hydrogenation separates
Device includes secondary hydrogenation aftercooler and secondary hydrogenation knockout drum.
Fig. 3 is the process units schematic diagram for comparing the carbon four plus hydrogen of embodiment.
Description of symbols:
Debutanizing tower 1, debutanizing tower condenser 2, debutanizing tower reboiler 3,4, one sections of debutanizing tower intermediate reboiler plus
8, one sections of circulating coolings of the cold knockout drum of hydrogen reactor 5, one-stage hydrogenation hot knock-out pot 6, one-stage hydrogenation aftercooler 7, one-stage hydrogenation/add
After hot device 9, second-stage hydrogenation reactor 10, secondary hydrogenation input and output material heat exchanger 11, secondary hydrogenation feed heater 12, secondary hydrogenation
The cold knockout drum 16 of cooler 13, secondary hydrogenation knockout drum 14, secondary hydrogenation hot knock-out pot 15, secondary hydrogenation, compressor suction tank 17,
Circulating hydrogen compressor 18, four raw material 19 of poor butylene carbon, rich four raw material 20 of butylene carbon, rich alkynes carbon 4 21, fresh hydrogen 22, not hydrogenating carbon
4 23, periodic off-gases 24, saturated carbon 4 25.
Specific embodiment
The preferred embodiment that the present invention will be described in more detail below with reference to accompanying drawings.
Embodiment 1
Carbon four plus hydrogen are carried out using four hydrogenation plant of carbon as shown in Figure 1.Described device includes: 1, one section of debutanizing tower and adds
5, one sections of circulating cooling/heaters 9 of hydrogen reactor, one-stage hydrogenation separator, second-stage hydrogenation reactor 10, secondary hydrogenation disengaging
Expect that heat exchanger 11, secondary hydrogenation feed heater 12, debutanizing tower intermediate reboiler 4, secondary hydrogenation separator, compressor are inhaled
Enter tank 17, circulating hydrogen compressor 18.
Poor four feeding line of butylene carbon and rich four feeding line of butylene carbon are separately connected debutanizing tower upper and lower part；
Debutanizing tower bottom connects 5 top of one-stage hydrogenation reactor after merging with rich alkynes carbon four；
Hydrogen feed line connects 5 top of one-stage hydrogenation reactor；
5 bottom of one-stage hydrogenation reactor connects one-stage hydrogenation separator, the connection compression of one-stage hydrogenation separation unit overhead
Machine suction tank；
Two-way is divided in one-stage hydrogenation separator bottom, all the way connect one section of circulating cooling/heater 9 after with rich alkynes carbon 4 21
Merge, then connects one-stage hydrogenation reactor 5；Another way merge with recycle hydrogen after connect secondary hydrogenation input and output material heat exchanger 11,
10 top of second-stage hydrogenation reactor is connected after secondary hydrogenation feed heater 12；
After 10 bottom of second-stage hydrogenation reactor connects secondary hydrogenation input and output material heat exchanger 11, debutanizing tower intermediate reboiler 4
Connect secondary hydrogenation hot knock-out pot 15；It is sequentially connected secondary hydrogenation aftercooler 13 at the top of secondary hydrogenation hot knock-out pot 15 and two sections add
Hydrogen-cooled knockout drum 16, is sequentially connected at the top of the cold knockout drum 16 of secondary hydrogenation after compressor suction tank 17, circulating hydrogen compressor 18 point
Two-way merges with the C-4-fraction pipeline from one-stage hydrogenation all the way, then connects secondary hydrogenation input and output material heat exchanger 11, another
Road connects 10 middle part of second-stage hydrogenation reactor；Cold 16 bottom of knockout drum of secondary hydrogenation connects secondary hydrogenation hot knock-out pot 15.
Method of hydrotreating is as follows:
(a) by out-of-bounds Lai poor butylene carbon four charging 19 and rich four raw material 20 of butylene carbon respectively enter 1 top of debutanizing tower
And lower part, it is separated through rectifying, 1 tower top of debutanizing tower obtains the raw material for alkylation for being rich in iso-butane, butene-1, isobutene, tower reactor
For the C 4 materials rich in normal butane, butene-2；
(b) 1 kettle material of debutanizing tower, 4 21, the one sections of cyclic carbons four of rich alkynes carbon out-of-bounds come and the fresh hydrogen out-of-bounds come
Gas reacts after being combined into 5 top of one-stage hydrogenation reactor, is monoolefine and saturated hydrocarbons by alkynes, diene hydrogenation；
(c) 5 bottom discharge of one-stage hydrogenation reactor enters one-stage hydrogenation separator, and the hydrogen isolated is sent to two sections and adds
The compressor suction tank of hydrogen, one-stage hydrogenation separator bottoms material are divided to two strands, one as recycle stock through one section circulation/it is cold
But heater 9 exchanges heat to return one-stage hydrogenation reactor 5, another burst of charging as secondary hydrogenation reaction after 20~80 DEG C；
(d) C-4-fraction after one-stage hydrogenation is mixed with two sections of recycle hydrogens through 11, two sections of secondary hydrogenation input and output material heat exchanger
Feed heater 12 enters second-stage hydrogenation reactor 10 by olefins hydrogenation and micro organic after being warming up to 100~300 DEG C
Sulphur nitrogen is converted into H2S and NH3；
(e) 10 bottom discharge of second-stage hydrogenation reactor passes through and secondary hydrogenation input and output material heat exchanger 11, debutanizing tower reboiler 4
After heat exchange is cooled to 50~100 DEG C, gas-liquid separation is carried out into secondary hydrogenation hot knock-out pot 15, top gas phase passes through secondary hydrogenation
Aftercooler 13 enters the cold knockout drum 16 of secondary hydrogenation after being cooled to 20~50 DEG C, connect compression at the top of the cold knockout drum 16 of secondary hydrogenation
Machine suction tank 17, bottom connect secondary hydrogenation hot knock-out pot 15, and 15 bottom of secondary hydrogenation hot knock-out pot is four product of saturated carbon.
Specific process conditions are as shown in table 1.
Embodiment 2
As shown in Fig. 2, difference from Example 1 is: reaction discharging exchanges heat through secondary hydrogenation input and output material heat exchanger 11
Afterwards, first enter secondary hydrogenation knockout drum 14 after secondary hydrogenation aftercooler 13 is cooled to 20~50 DEG C and carry out gas-liquid separation, top
Gas phase connects circulating hydrogen compressor suction tank 17, and bottom liquid phases are the extraction of four product of saturated carbon.
Comparative example 1
As shown in figure 3, difference from Example 2 is: not set debutanizing tower intermediate reboiler 4.
Table 1
By above-mentioned apparatus and process, the comprehensive energy consumption of embodiment 1-2 is 35MJ/t carbon four, compares comparative example 1, energy
Save 15% or more energy consumption.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive.Not inclined
In the case where scope and spirit from illustrated each embodiment, many is repaired for those skilled in the art
Change and change will be apparent from.
Claims (11)
1. the process units of a kind of carbon four plus hydrogen, it is characterised in that:
Described device includes: debutanizing tower, one-stage hydrogenation reactor, one section of circulating cooling/heater, one-stage hydrogenation separation dress
Set, second-stage hydrogenation reactor, secondary hydrogenation input and output material heat exchanger, secondary hydrogenation feed heater, debutanizing tower intermediate reboiler,
Secondary hydrogenation separator, compressor suction tank, circulating hydrogen compressor；Wherein,
Poor four feeding line of butylene carbon and rich four feeding line of butylene carbon are separately connected debutanizing tower upper and lower part；
Debutanizing tower bottom outlet connects one-stage hydrogenation reactor top after merging with rich four feeding line of alkynes carbon；
Hydrogen feed line connects one-stage hydrogenation reactor top；
One-stage hydrogenation reactor bottom connects one-stage hydrogenation separator, the sucking of one-stage hydrogenation separation unit overhead connect compressor
Tank；
One-stage hydrogenation separator bottom outlet divides two-way, all the way connect one section of circulating cooling/heater after with rich alkynes carbon
Four merge, and then connect one-stage hydrogenation reactor；Another way is sequentially connected the heat exchange of secondary hydrogenation input and output material after merging with recycle hydrogen
Second-stage hydrogenation reactor top is connected after device, secondary hydrogenation feed heater；
Add for two sections of connection after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Hydrogen separator；
Secondary hydrogenation separator be sequentially connected after compressor suction tank, circulating hydrogen compressor with the carbon four from one-stage hydrogenation into
Expects pipe line merges, and then connects secondary hydrogenation input and output material heat exchanger.
2. the process units of carbon four as described in claim 1 plus hydrogen, it is characterised in that:
Circulating hydrogen compressor outlet line divides two-way, and two sections are connected after merging all the way with the C-4-fraction pipeline from one-stage hydrogenation
Add hydrogen input and output material heat exchanger, another way connects in the middle part of second-stage hydrogenation reactor.
3. the process units of carbon four as described in claim 1 plus hydrogen, it is characterised in that:
The one-stage hydrogenation separator includes one-stage hydrogenation hot knock-out pot, one-stage hydrogenation aftercooler and the cold separation of one-stage hydrogenation
Tank.
4. the process units of carbon four as described in claim 1 plus hydrogen, it is characterised in that:
The secondary hydrogenation separator is using one of following two mode:
A) the secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and the cold separation of secondary hydrogenation
Tank；
Add for two sections of connection after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Hydrogen hot knock-out pot, is sequentially connected secondary hydrogenation aftercooler and the cold knockout drum of secondary hydrogenation at the top of secondary hydrogenation hot knock-out pot, and two sections
Add connect compressor suction tank at the top of hydrogen-cooled knockout drum；The cold knockout drum bottom of secondary hydrogenation connects secondary hydrogenation hot knock-out pot；
B) the secondary hydrogenation separator includes adding secondary hydrogenation aftercooler and secondary hydrogenation knockout drum；
Two are sequentially connected after second-stage hydrogenation reactor bottom connection secondary hydrogenation input and output material heat exchanger, debutanizing tower intermediate reboiler
Section plus hydrogen aftercooler and secondary hydrogenation knockout drum, secondary hydrogenation knockout drum top connect compressor suction tank.
5. the process units of carbon four plus hydrogen as described in any one of claim 1-4, it is characterised in that: the secondary hydrogenation
Feed heater is electric heater, steam heater or heating furnace.
6. a kind of four method of hydrotreating of carbon using the process units as described in any one of claim 1-5, which is characterized in that institute
The method of stating includes:
Poor butylene carbon four and rich butylene carbon four respectively enter debutanizing tower upper and lower part, and through separating, debutanization tower top is obtained not
Hydrogenating carbon four, kettle material obtain saturated carbon four after merging with rich alkynes carbon four after one-stage hydrogenation, secondary hydrogenation.
7. four method of hydrotreating of carbon as claimed in claim 6, which is characterized in that the described method includes:
(a) poor butylene carbon four and rich butylene enter via poor four feeding line of butylene carbon and rich four feeding line of butylene carbon de- respectively
Butane tower upper and lower part, through separating, debutanization tower top obtains not hydrogenating carbon four；
(b) debutanization kettle material, four, the one sections of cyclic carbons four of rich alkynes carbon out-of-bounds come and the fresh hydrogen out-of-bounds come enter one section
Alkynes, diene hydrogenation are monoolefine and saturated hydrocarbons by hydrogenator reaction；
(c) one-stage hydrogenation reactor bottom discharging enters one-stage hydrogenation separator, and the hydrogen isolated is sent to secondary hydrogenation
Compressor suction tank, one-stage hydrogenation separator bottoms material are divided to two strands, one adds as recycle stock through one section of circulation/cooling
One-stage hydrogenation reactor, another burst of charging as secondary hydrogenation reaction are returned after hot device heat exchange；
(d) as the C-4-fraction after the one-stage hydrogenation of secondary hydrogenation reaction feed, the recycle hydrogen come with circulating hydrogen compressor is mixed
It closes and is saturated monoolefin hydrogenation simultaneously into second-stage hydrogenation reactor after secondary hydrogenation input and output material heat exchanger, two section feeding heaters
Remove sulphur nitrogen impurity；
(e) second-stage hydrogenation reactor bottom discharge enters secondary hydrogenation separator after secondary hydrogenation input and output material heat exchanger, point
The hydrogen separated out enters circulating hydrogen compressor, and secondary hydrogenation separator bottom obtains adding the saturated carbon four after hydrogen；
(f) through circulating hydrogen compressor after secondary hydrogenation separation unit overhead hydrogen merges with one-stage hydrogenation separation unit overhead hydrogen
Boosting is used as two sections of circulating hydrogens, and two sections of circulating hydrogens are divided to two strands, one is merged into the C-4-fraction after one-stage hydrogenation
Enter two sections of input and output material heat exchangers, another strand enters in the middle part of second-stage hydrogenation reactor.
8. four method of hydrotreating of carbon as claimed in claim 7, it is characterised in that:
In step (e), when secondary hydrogenation separator includes secondary hydrogenation hot knock-out pot, secondary hydrogenation aftercooler and secondary hydrogenation
When cold knockout drum, the hydrogenated input and output material heat exchanger of second-stage hydrogenation reactor bottom discharge, the heat exchange of debutanizing tower reboiler are cooled to
Enter secondary hydrogenation hot knock-out pot after 50~100 DEG C, secondary hydrogenation hot knock-out pot top gas phase is cold by secondary hydrogenation aftercooler
But to entering the cold knockout drum of secondary hydrogenation after 20~50 DEG C.
9. four method of hydrotreating of carbon as claimed in claim 7, it is characterised in that:
In step (e), when secondary hydrogenation separator includes secondary hydrogenation aftercooler and secondary hydrogenation knockout drum, secondary hydrogenation
After the hydrogenated input and output material heat exchanger of reactor bottom material, the heat exchange of debutanizing tower reboiler, then through adding secondary hydrogenation aftercooler cold
But to entering secondary hydrogenation knockout drum after 20~50 DEG C.
10. four method of hydrotreating of carbon as described in any one of claim 6-9, it is characterised in that:
The operating condition of debutanizing tower includes: that pressure is 0.2~1.0MPaG, and tower top operation temperature is 20~80 DEG C, and the number of plates is
50~200, reflux ratio is 1~20；
The one-stage hydrogenation reactor be trickle bed reactor, reactor inlet temperature be 20~80 DEG C, pressure be 1.5~
4.5MPaG, reaction temperature rising are 5~100 DEG C, and hydrogen/oil mol ratio is 0.2~5, and catalyst volume air speed is 0.5~6h-1, catalyst
For palladium system or nickel catalyst；
The second-stage hydrogenation reactor be fixed bed reactors, reactor inlet temperature be 100~300 DEG C, pressure be 1.5~
4.5MPaG, reaction temperature rising are 5~150 DEG C, and hydrogen/oil mol ratio is 0.2~5, and liquid volume air speed is 0.5~6h-1, catalyst is
Palladium system or molybdenum nickel catalyst.
11. four method of hydrotreating of carbon as described in any one of claim 6-9, it is characterised in that: the carbon four is rich in carbon
The liquefied gas of four alkynes or alkadienes and monoolefine, associated gas, refinery C four or ethylene unit carbon-4.
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| CN116023350A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | System and method for preparing succinic anhydride |
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