CN106608805B - A kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons - Google Patents
A kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons Download PDFInfo
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- CN106608805B CN106608805B CN201510696786.XA CN201510696786A CN106608805B CN 106608805 B CN106608805 B CN 106608805B CN 201510696786 A CN201510696786 A CN 201510696786A CN 106608805 B CN106608805 B CN 106608805B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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Abstract
The invention discloses a kind of methods of liquid phase selective hydrogenation of C 3 hydrocarbons, carry out selection plus hydrogen this method comprises: contacting after the fresh C3 fraction a containing propine and/or allene produced from the depropanizing tower of propylene production technology, cyclic carbon three logistics b and hydrogen c are mixed with selective hydrogenation catalyst；Selection plus hydrogen resulting material are carried out gas-liquid separation to obtain containing propylene, the gaseous stream g of propane and liquid phase stream h containing propylene, propane；The liquid phase stream h containing propylene, propane is divided into first part logistics i and second part logistics j, first part logistics i is as the three logistics b of cyclic carbon；Second part logistics j returns to depropanizing tower.The propine and/or allene being not only effectively stripped of using method provided by the invention in C3 fraction, while energy consumption is reduced, with the superiority that the prior art is incomparable.
Description
Technical field
The present invention relates to a kind of methods of liquid phase selective hydrogenation of C 3 hydrocarbons.
Background technique
Petroleum hydrocarbon steam cracking is to prepare the most important method of the olefin monomers such as propylene.It is generated during production of propylene
Alkynes and alkadienes be influence propylene polymerization objectionable impurities, they can inhibit the activity of catalyst for polymerization of propylene, increase
Add the consumption of catalyst, the property of acrylic polymers product is reduced, so must be removed.Industrially generally use catalysis choosing
Select the alkynes and alkadienes in hydrogenation method and solvent absorption removing cracking gas.Catalysis selective hydrogenation method process flow is simple, and third
Alkene selectivity is high, and by-pass product is few, is the prefered method of green chemistry process without environmental pollution, application is more prevalent.
US4571442A (1986) discloses a kind of acetylene liquid phase selective hydrogenation technique, by the hydrogen to be added containing acetylene and ethylene
Fraction is dissolved in a kind of compositions of hydrocarbons diluent, the liquid of formation is then sent into hydrogenator together with hydrogen, anti-
It answers in device and liquid phase selective hydrogenation is carried out by the catalyst bed of supported palladium on an aluminium oxide from the top down.Gas-liquid obtained
Mixture is sent into flash tank after heat exchanger is cooling, and purified gas fraction is separated with liquid diluent in flash tank.Point
Liquid diluent from after can be recycled.Liquid diluent include at least one aromatic hydrocarbons and it is at least one selected from primary amine,
The amine compounds of secondary amine and polyamine.
GB1175709A (1969) discloses a kind of liquid phase catalytic hydrogenation equipment for benzene hydrogenation at hexamethylene.In the liquid
In body catalytic hydrogenation equipment, hydrogen and liquid introduce hydrogenator, pass through the catalyst bed and orifice plate on reactor top, gas
It is mutually separated in the gas phase separation chamber in portion in the reactor, reactor is discharged by pipeline, and liquid phase continues through reactor
The catalyst bed and orifice plate of lower part, contact with the hydrogen of reverse flow, and the liquid after adding hydrogen is flowed out from reactor bottom.By gas
The gas of phase phase separation chamber discharge successively passes through cooler after two heat exchangers, and the liquid component to gasify in mixture is cold
But it is condensed into liquid in device, generates biphase gas and liquid flow, enters back into separator.In the separator, gas phase and liquid phase separation.
CN101139242B discloses a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons.Contain propine and/or allene
C3 fraction mixed with hydrogen after, mixture obtained at the top of selective hydrogenation reaction device by entering, from top to bottom by anti-
The selective hydrogenation catalyst bed in device is answered, is contacted with selective hydrogenation catalyst.The heat drawn from selective hydrogenation reaction device bottom
Discharging (liquids and gases mixture) it is cooling without heat exchanger and/or cooler, be directly entered knockout drum and carry out gas
Liquid separation.Gas phase portion enters one and is placed in the condenser of knockout drum top or top, and draws condensed liquid
Enter subsequent processing as product, uncooled gas phase is vented or is sent to fuel gas pipe network or is sent to two sections of compressor, three sections
Or four sections of entrances, selective hydrogenation reaction device is adjusted by the gas phase flow rate of temperature and/or control emptying in control condenser
Interior pressure.From knockout drum come out liquid material in a part mixed with fresh C3 fraction after, enter together
Hydrogenator, another part are sent to propylene rectification tower as product.
In traditional hydrocarbon steam cracking separating technology, the method for liquid phase selective hydrogenation of C 3 hydrocarbons is: from depropanizing tower
The fresh C3 fraction containing propine and allene for pushing up extraction, through matching hydrogen, into selective hydrogenation reaction device, in hydrogenator
Equipped with three liquid phase selective hydrogenation catalyst of carbon, charging passes through selective hydrogenation catalyst bed, selective hydrogenation reaction device from the top down
The liquid discharging of bottom needs to reduce temperature through cooler, and the liquid after cooling enters knockout drum and carries out gas phase and liquid phase
Separation, gas phase is vented or is sent to fuel gas pipe network or is sent to two sections, three sections or four sections entrances of compressor, a part of liquid after separation
Phase logistics is recycled, and mixes with fresh C3 fraction；Another part liquid phase stream is sent to propylene rectification tower as product output
It is refined.Traditional handicraft adjusts hydrogenator generally by knockout drum gas phase air compensation (or emptying amount) is adjusted
Interior pressure.
It is usually necessary to use one section, two sections or three sections series connection for existing liquid phase selective hydrogenation of C 3 hydrocarbons catalyst bed
Or be arranged in parallel, structure is complicated for this hydrogenator, and can only by reactor feed propine and/or allene remove
To within 1000ppm.The removing degree of this propine and/or allene is all difficult to receive to most of factories, and factory generally needs
Propine and/or allene are removed to 200ppm or less.
Summary of the invention
For prior art liquid phase selective hydrogenation of C 3 hydrocarbons method cannot effectively remove propine in C3 fraction and/
Or allene, liquid phase selective hydrogenation of C 3 hydrocarbons complex procedures and the defect that energy consumption is high, the present invention provide a kind of new carbon three and evaporate
Divide the method for liquid phase selective hydrogenation.Method provided by the present invention not only simplifies liquid phase selective hydrogenation of C 3 hydrocarbons process, drop
Low energy consumption of reaction, and improve the removal effect of propine and/or allene.
The present invention provides a kind of method of new liquid phase selective hydrogenation of C 3 hydrocarbons, method includes the following steps:
(1) the fresh C3 fraction containing propine and/or allene that will be produced from the depropanizing tower of propylene production technology
A, three logistics b of cyclic carbon and hydrogen c mixing after in the case where select hydroconversion condition, in selective hydrogenation reaction device with select hydrogenation catalyst
Agent contact carries out selection plus hydrogen；
(2) hydrogenation material obtained by step (1) is subjected to gas-liquid separation, obtain containing propylene, propane gaseous stream g and contain
There is the liquid phase stream h of propylene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into first part logistics i and second part logistics j, the
A part of logistics i is as the three logistics b of cyclic carbon；Second part logistics j returns to depropanizing tower.
Method provided by the invention is simplifying liquid phase selective hydrogenation of C 3 hydrocarbons process, reduces the same of energy consumption of reaction
When, improve the removal effect of propine and/or allene.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the flow chart of liquid phase selective hydrogenation of C 3 hydrocarbons in embodiment 1；
Fig. 2 is the flow chart of liquid phase selective hydrogenation of C 3 hydrocarbons in comparative example 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods of liquid phase selective hydrogenation of C 3 hydrocarbons, method includes the following steps:
(1) the fresh C3 fraction containing propine and/or allene that will be produced from the depropanizing tower of propylene production technology
A, three logistics b of cyclic carbon and hydrogen c mixing after in the case where select hydroconversion condition, in selective hydrogenation reaction device with select hydrogenation catalyst
Agent contact carries out selection plus hydrogen；
(2) hydrogenation material obtained by step (1) is subjected to gas-liquid separation, obtain containing propylene, propane gaseous stream g and contain
There is the liquid phase stream h of propylene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into first part logistics i and second part logistics j, the
A part of logistics i is as the three logistics b of cyclic carbon；Second part logistics j returns to depropanizing tower.
In the present invention, preferably will first be produced from the depropanizing tower of propylene production technology in step (1) containing propine and/
Or it after the completion of fresh C3 fraction a and three logistics b of the cyclic carbon mixing of allene, is mixed with hydrogen c.
In accordance with the present invention it is preferred that the fresh C3 fraction a is during production of propylene by sequence separation process
Depropanization overhead extraction contain propylene, propane, propine and/or allene, it is also possible to contain a small amount of cyclopropane, a small amount of carbon four
The C3 fraction of the above component.
In accordance with the present invention it is preferred that the molar content of propine and/or allene is 0.2- in the fresh C3 fraction a
8%.
In the present invention, hydrogenation material obtained by step (1) can be introduced directly into knockout drum and carry out gas-liquid separation,
Hydrogenation material obtained by step (1) can be obtained into gaseous stream and liquid phase object after selective hydrogenation reaction device carries out pre-separation first
Stream, and gaseous stream and liquid phase stream are introduced into knockout drum respectively and carry out gas-liquid separation.
In accordance with the present invention it is preferred that hydrogenation material obtained by step (1), which is carried out gas-liquid separation, includes: in step (2)
1] gained hydrogenation material is subjected to pre-separation in selective hydrogenation reaction device and obtains gaseous stream e and liquid phase stream f；
2] the gaseous stream e and liquid phase stream f are introduced into knockout drum progress gas-liquid separation respectively and obtain described contain
There are propylene, the gaseous stream g of propane and the liquid phase stream h containing propylene, propane.
Compared with prior art, using this preferred embodiment, the effect of hydrogenation material gas-liquid separation obtained by step (1) is enabled to
Fruit is more preferable.
In the present invention, the gaseous stream g can contain a small amount of propine and/or allene, can also not contain third
Alkynes and allene.
In the present invention, the liquid phase stream h can contain a small amount of propine and/or allene, can also not contain third
Alkynes and allene.
In accordance with the present invention it is preferred that the selective hydrogenation reaction device includes the selective hydrogenation catalyst bed positioned at middle and upper part
Layer, the pre-separation tank positioned at selective hydrogenation reaction device middle and lower part, the liquid phase stream f positioned at selective hydrogenation reaction device bottom are exported,
The outlet gaseous stream e and top feed mouth positioned at middle and lower part, wherein contain what is produced from the depropanizing tower of propylene production technology
Have propine and/or allene fresh C3 fraction a, cyclic carbon three logistics b and hydrogen c mixing after from the top feed mouth into
Enter after being contacted with the selective hydrogenation catalyst bed, carries out the pre-separation into gas-liquid pre-separation tank.
In accordance with the present invention it is preferred that the gaseous stream e that pre-separation is obtained is from positioned at selective hydrogenation reaction device middle and lower part
Gaseous stream e is drawn outlet, and the liquid phase stream f that pre-separation obtains goes out from the liquid phase stream f for being located at selective hydrogenation reaction device bottom
Mouth is drawn.
In accordance with the present invention it is preferred that the gaseous stream e and liquid phase stream f are introduced between gas without subcooler
Liquid knockout drum carries out gas-liquid separation.Using this preferred embodiment, while guaranteeing technical effect, energy consumption is reduced, operation is more
Simply.
In accordance with the present invention it is preferred that the pressure of the knockout drum is 1-4MPa.
In accordance with the present invention it is preferred that first part's logistics i adds as the three logistics b of cyclic carbon back to selection
It is directly mixed with fresh C3 fraction a when hydrogen reactor without supercooling.
In accordance with the present invention it is preferred that the fresh C3 fraction a needs not move through heater to improve temperature.
In the present invention, do not have since the liquid phase stream of selective hydrogenation reaction device bottom discharge is directly entered knockout drum
By heat exchanging process, do not cool down, so a part in the liquid phase stream of selective hydrogenation reaction device bottom discharge is through gas-liquid
When being recycled to selective hydrogenation reaction device entrance after separation, for improving the fresh C3 fraction a temperature of selective hydrogenation reaction device entrance
Can heating load it is more, therefore, those skilled in the art, which can pass through, adjusts three logistics b of cyclic carbon and fresh C3 fraction a
Flow-rate ratio carrys out the temperature of control selections hydrogenator entrance C3 fraction.
As needed, if the shortage of heat that three logistics b of cyclic carbon is provided, can also be added by heater to selection is entered
The material of hydrogen reactor is heated.Liquid phase selective hydrogenation of C 3 hydrocarbons operation is substantially increased using method provided by the invention
Flexibility.
In accordance with the present invention it is preferred that the flow-rate ratio of step (1) three logistics b of the cyclic carbon and fresh C3 fraction a is
0.01-1:1, preferably 0.2-0.8:1.
In the present invention, the liquid phase stream h containing propylene, propane is divided into first part logistics i and by step (3)
Two fraction of stream j, first part logistics i are as the three logistics b of cyclic carbon；Second part logistics j returns to depropanizing tower.
First part logistics i is transported to selective hydrogenation reaction device entrance by pump with propine in the charging of diluting reactor entrance
And/or the content of allene, the flow for adjusting first part's logistics i can be with the stream of control selections hydrogenator inlet feed
Amount and temperature.
Second part logistics j returns to depropanizing tower, can reduce propine and/or allene in depropanizing tower charging
Concentration, moreover it is possible to increase the separating effect of depropanizing tower, reduce energy consumption.
Distribution of the present invention by adjusting liquid phase stream h between first part logistics i and second part logistics j, thus
It being capable of more flexible adjusting three logistics flux of carbon, temperature and the propine of selective hydrogenation reaction device entrance and/or containing for allene
Amount, the propine and/or allene being more advantageous in removing C3 fraction.
In the present invention, those skilled in the art can be by specifically needing logistics i's described to step (3) and logistics j
Flow-rate ratio is adjusted, with flow, temperature and the propine of selective hydrogenation reaction device entrance required for obtaining and/or allene
Content.
It should be noted that the larger fluctuation of the flow of second part logistics j should be avoided, in order to avoid cause depropanizing tower
Excessive operation fluctuation.
In accordance with the present invention it is preferred that the flow-rate ratio of step (3) the logistics i and logistics j is 0.01-2:1, preferably
0.2-1:1.
In the present invention, it is preferred to the gaseous stream g containing propylene, propane that gas-liquid separation is obtained be drawn out to it is subsequent
Propylene rectification tower is further processed.
In accordance with the present invention it is preferred that the pressure of the selective hydrogenation reaction device is by being drawn out to subsequent propylene rectifying column
The flow of gaseous stream g is adjusted.
In the present invention, there is no special restriction for the selection hydroconversion condition in selective hydrogenation reaction device, can be this
The selection hydroconversion condition of field routine, it is preferable that the selection hydroconversion condition in the selective hydrogenation reaction device includes: hydrogen alkynes mole
It is 0.5-2, reaction pressure 1-4MPa, entrance than (i.e. the molar ratio of propine and/or allene in hydrogen and C3 fraction)
Temperature is 5-50 DEG C, outlet temperature is 20-80 DEG C, and the molar content of propine and/or allene is 0- in gaseous stream g
500ppm。
In the present invention, the selective hydrogenation catalyst can select to add for any C3 fraction liquid phase that can be used in this field
The catalyst of hydrogen.
Preferably, the selective hydrogenation catalyst includes carrier and the main active component that is supported on carrier, the carrier
Selected from one of aluminium oxide, silica, titanium oxide, zinc oxide, molecular sieve, silicon carbide, calcium carbonate, kaolin and cordierite or
A variety of, the main active component element is selected from least one of palladium, ruthenium and platinum element.
Preferably, the selective hydrogenation catalyst further includes the active component that helps being supported on carrier, described to help active group
Point element in alkali metal element, alkali earth metal, transition metal element, rare earth element and V A race metallic element one
Kind is a variety of, preferably in silver, copper, zinc, potassium, sodium, magnesium, calcium, beryllium, tin, lead, cadmium, strontium, barium, radium, manganese, zirconium, molybdenum and Germanium
It is one or more.
In accordance with the present invention it is preferred that on the basis of the total amount of selective hydrogenation catalyst, based on the element, the main active group
The content divided is 0.01-1 weight %, and preferably 0.01-0.5 weight %, the content for helping active component is 0.01-2 weight
Measure %, preferably 0.01-1 weight %.
Compared with the method for traditional liquid phase selective hydrogenation of C 3 hydrocarbons, liquid phase selective hydrogenation of C 3 hydrocarbons of the invention
Method advantage can be summarized as follows:
1, in traditional liquid phase selective hydrogenation of C 3 hydrocarbons technique, selective hydrogenation reaction device bottom discharge is cold through subcooler
But, it enters back into knockout drum and carries out gas-liquid two-phase separation.Since discharging is first cooled down, liquid material a part of extraction
Also need to heat after into subsequent propylene rectifying column, the liquid material that another part is recycled to selective hydrogenation reaction device entrance improve into
Mouthful fresh material temperature can heating load it is less, thus energy utilization is unreasonable, and energy consumption is larger, and operation difficulty is larger.The present invention
In the technique of the liquid phase selective hydrogenation of C 3 hydrocarbons of offer, the discharging of selective hydrogenation reaction device Base Heat is entering knockout drum
Before, discharge method is distinguished using special liquid phase, gas phase, ensure that three selective hydrogenation reaction device of carbon is in drip bed operating mould
Formula, the outlet temperature for keeping selective hydrogenation reaction device constant by the gasification of carbon 3 material in reaction process, passes through side gas phase
Discharging prevents catalyst to be submerged to guarantee liquid level not superelevation.Due to selective hydrogenation reaction device bottom discharge liquid directly into
Enter knockout drum and do not pass through heat exchanging process, do not cool down, so in the liquid of selective hydrogenation reaction device bottom discharge
When a part is recycled to selective hydrogenation reaction device entrance after gas-liquid separation, for improving selective hydrogenation reaction device entrance delivered fresh
Material temperature degree can heating load it is more.Therefore, method of the invention simplifies conventional process flow, and low energy consumption, operates more convenient.
2, in traditional liquid phase selective hydrogenation of C 3 hydrocarbons technique, selection is adjusted by the way of knockout drum tonifying Qi and is added
The pressure of hydrogen reactor generally carries out tonifying Qi using hydrogen, sometimes results in bringing into for excessive hydrogen in this way, be unfavorable for subsequent
Propylene distillation operation.Method of the invention is the flow by directly adjusting the gaseous stream g for being drawn out to subsequent propylene rectifying column
To adjust the pressure of selective hydrogenation reaction device, the controllability of raising liquid phase selective hydrogenation of C 3 hydrocarbons reaction process.
3, traditional C 3 fraction selective hydrogenation process adjustments means are few, especially third when selection hydrogenator entrance
When alkynes and/or higher allene content, selective hydrogenation reaction device entrance propine and/or the third two can not be diluted effectively still at present
Alkene content is to guarantee the measure for suitably exporting propine and/or allene content requirement.The present invention is existed by adjusting liquid phase stream h
Distribution between first part logistics i and second part logistics j enters the selection of carbon three plus hydrogen so as to more flexible adjust
The content of three logistics flux of carbon of reactor inlet, temperature and propine and/or allene is more advantageous in removing C3 fraction
Propine and/or allene.
4, method provided by the invention can be replaced with single hop bed hydroprocessing mode used by the prior art one section, two sections,
Three sections of serial or parallel connections add the mode of hydrogen, and three liquid phase of the carbon selection in method provided by the invention and conventional hydrocarbon-based cracking technology adds
The advantages that hydrogen methods compare, and have energy utilization more reasonable, low equipment investment, product quality is controllable.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated beneficial effect, it is intended to help
Where reader more clearly understands Spirit Essence of the invention, but any restriction cannot be constituted to practical range of the invention.
Embodiment 1
According to the process of three liquid phase selective hydrogenation of carbon of the invention shown in FIG. 1.
Carbon 3 material f0 is reacted to the resulting material f1 by depropanizing tower S0 overhead extraction in depropanizing tower S0 through pumping
S1 passes sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (flow 180t/h, propine and allene mole contain
Amount the sum of for 3%), three logistics b (flow 90t/h) of cyclic carbon mixing after, mixed with hydrogen c (hydrogen flowing quantity 380kg/h,
Hydrogen purity is 95%, and other impurity are methane) after S3 exchanges heat, mixture d obtained is by selective hydrogenation reaction device top
Into reactor, from top to bottom by the selective hydrogenation catalyst bed R1 in selective hydrogenation reaction device, selected with three liquid phase of carbon
Hydrogenation catalyst contact (catalyst is the BC-L-83 that middle petrochemical industry Beijing Chemical Research Institute provides), reactor pressure is
2.40MPa, reactor inlet temperature are 38 DEG C, and reactor outlet temperature is 60 DEG C.
After carrying out selective hydrogenation reaction, gained hydrogenation material is carried out in the pre-separation tank S4 in selective hydrogenation reaction device
Pre-separation obtains gaseous stream e and liquid phase stream f, middle and upper part, liquid phase stream by gaseous stream e by selective hydrogenation reaction device
F is drawn out to knockout drum S5 by the bottom of selective hydrogenation reaction device respectively and carries out gas-liquid two-phase separation, knockout drum S5
Pressure is 2.40MPa.Knockout drum S5 and reboiler S6 are shared, obtained gaseous stream g (propine and allene molar content
Less than 200ppm) enter propylene rectification tower, the flow of gaseous stream g is 90t/h, and the gas phase of propylene rectification tower is entered by adjusting
The pressure of selective hydrogenation reaction device is adjusted to 2.4MPa by the flow of logistics g；Obtained first part's logistics in liquid material h
I is mixed into selective hydrogenation reaction with fresh C3 fraction a through pump S7 conveying as three logistics b (flow 90t/h) of cyclic carbon
Device, the second part logistics j in liquid material h that gas-liquid separation obtains return to depropanizing tower S0, and the flow of liquid phase stream j is
100t/h。
Using method provided by the present embodiment, is simplifying liquid phase selective hydrogenation of C 3 hydrocarbons process, reducing energy consumption
While, so that propine and allene molar content are less than 200ppm in gained gaseous stream g after gas-liquid separation.
Comparative example l
According to the process of traditional three liquid phase selective hydrogenation of carbon shown in Fig. 2.
Carbon 3 material f0 is reacted to the resulting material f1 by depropanizing tower S0 overhead extraction in depropanizing tower S0 through pumping
S1 passes sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (propine and allene molar content are 3%, and flow is
It 180t/h) is mixed with hydrogen c, hydrogen flowing quantity 380kg/h, hydrogen purity 95%, mixture d obtained is by selection plus hydrogen
Enter selective hydrogenation reaction device at the top of reactor R1, from top to bottom by the selective hydrogenation catalyst bed in reactor, with carbon
Three liquid phase selective hydrogenation catalyst contact (BC-L-83 that middle petrochemical industry Beijing Chemical Research Institute provides), reactor pressure is
2.40MPa, reactor inlet temperature are 38 DEG C, and reactor outlet temperature is 60 DEG C.
After carrying out selective hydrogenation reaction, it is cold that selective hydrogenation reaction device R1 bottom discharge m is introduced into a cooler S9 progress
But, it enters back into a knockout drum S5 and carries out gas-liquid two-phase separation, knockout drum S5 pressure is 2.40MPa.Gas-liquid separation
Gaseous stream g emptying afterwards, passes through from a part of i in the liquid stream h that knockout drum S5 comes out as three recycle stock of carbon
S7 conveying is pumped, is mixed into reactor with fresh C3 fraction a after heat exchanger S8 heat exchange, three circular flow of carbon is 90t/h；
Another part n is sent to propylene rectification tower as product and is refined, and the flow of liquid phase stream n is 100t/h, third in liquid phase stream n
The molar content of alkynes and allene is about 1000ppm.
Embodiment 2
According to method described in embodiment 1, the difference is that the flow of fresh C3 fraction a is 210t/h, three object of cyclic carbon
The flow for flowing b is 100t/h, and the flow of gaseous stream g is 110t/h, correspondingly, entering the gas phase of propylene rectification tower by adjusting
The pressure of selective hydrogenation reaction device is adjusted to 2.35MPa by the flow of logistics g.
Using method provided by the present embodiment, so that propine and allene rub in gained gaseous stream g after gas-liquid separation
You are less than 200ppm at content.
Embodiment 3
According to the process of three liquid phase selective hydrogenation of carbon of the invention shown in FIG. 1.
Carbon 3 material f0 is reacted to the resulting material f1 by depropanizing tower S0 overhead extraction in depropanizing tower S0 through pumping
S1 passes sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (flow 150t/h, propine and allene mole contain
2.5%) the sum of amount is, after three logistics b (flow 75t/h) of cyclic carbon mixing, (hydrogen flowing quantity 290kg/ is mixed with hydrogen c
H, hydrogen purity 95%, other impurity are methane) after S3 exchanges heat, mixture d obtained is by selective hydrogenation reaction device top
Portion enters reactor, from top to bottom by the selective hydrogenation catalyst bed R1 in selective hydrogenation reaction device, selects with three liquid phase of carbon
Hydrogenation catalyst contact (catalyst is the BC-L-83 that middle petrochemical industry Beijing Chemical Research Institute provides) is selected, reactor pressure is
2.35MPa, reactor inlet temperature are 40 DEG C, and reactor outlet temperature is 58 DEG C.
After carrying out selective hydrogenation reaction, gained hydrogenation material is carried out in the pre-separation tank S4 in selective hydrogenation reaction device
Pre-separation obtains gaseous stream e and liquid phase stream f, middle and upper part, liquid phase object by gaseous stream e by selective hydrogenation reaction device R1
Stream f is drawn out to knockout drum S5 by the bottom of selective hydrogenation reaction device R1 respectively and carries out gas-liquid two-phase separation, gas-liquid separation
Tank S5 pressure is 2.35MPa.Knockout drum S5 and reboiler S6 are shared, obtained gaseous stream g (propine and allene mole
Content is less than 100ppm) enter propylene rectification tower, the flow of gaseous stream g is 80t/h, enters propylene rectification tower by adjusting
The pressure of selective hydrogenation reaction device is adjusted to 2.35MPa by the flow of gaseous stream g；First obtained in liquid material h
Point logistics i as three logistics b (flow 75t/h) of cyclic carbon through pump S7 conveying and fresh C3 fraction a be mixed into selection plus
Hydrogen reactor, the second part logistics j in liquid material h that gas-liquid separation obtains return to depropanizing tower S0, liquid phase stream j's
Flow is 80t/h.
Using method provided by the present embodiment, so that propine and allene rub in gained gaseous stream g after gas-liquid separation
You are less than 100ppm at content.
Comparative example 2
According to the process of traditional three liquid phase selective hydrogenation of carbon shown in Fig. 2.
Carbon 3 material f0 is reacted to the resulting material f1 by depropanizing tower S0 overhead extraction in depropanizing tower S0 through pumping
S1 passes sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (propine and allene molar content are 2.5%, flow
It is mixed for 150t/h) with hydrogen c, hydrogen flowing quantity 290kg/h, hydrogen purity 95%, mixture d obtained is added by selection
Enter selective hydrogenation reaction device at the top of hydrogen reactor R1, passes through the selective hydrogenation catalyst bed in reactor from top to bottom, with
Three liquid phase selective hydrogenation catalyst of carbon contact (BC-L-83 that middle petrochemical industry Beijing Chemical Research Institute provides), reactor pressure is
2.35MPa, reactor inlet temperature are 40 DEG C, and reactor outlet temperature is 58 DEG C.
After carrying out selective hydrogenation reaction, it is cold that selective hydrogenation reaction device R1 bottom discharge m is introduced into a cooler S9 progress
But, it enters back into a knockout drum S5 and carries out gas-liquid two-phase separation, knockout drum S5 pressure is 2.35MPa.Gas-liquid separation
Gaseous stream g emptying afterwards, passes through from a part of i in the liquid stream h that knockout drum S5 comes out as three recycle stock of carbon
S7 conveying is pumped, is mixed into reactor with fresh C3 fraction a after heat exchanger S8 heat exchange, three circular flow of carbon is 75t/h；
Another part n is sent to propylene rectification tower as product and is refined, and the flow of liquid phase stream n is 80t/h, third in liquid phase stream n
The molar content of alkynes and allene is about 500ppm.
Embodiment 1 and comparative example 1, embodiment 3 and comparative example 2 are compared as can be seen that C3 fraction provided by the invention
Liquid phase selective hydrogenation method is not only effectively stripped of propine and/or allene in C3 fraction, while reducing energy consumption, has
The incomparable superiority of the prior art.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons, method includes the following steps:
(1) by the fresh C3 fraction a containing propine and/or allene produced from the depropanizing tower of propylene production technology, follow
After ring carbon three logistics b and hydrogen c mixing in the case where selecting hydroconversion condition, connect in selective hydrogenation reaction device with selective hydrogenation catalyst
Touching carries out selection plus hydrogen, and the flow-rate ratio of the three logistics b of cyclic carbon and fresh C3 fraction a is 0.01-1:1；
(2) hydrogenation material obtained by step (1) is subjected to gas-liquid separation, obtain containing propylene, propane gaseous stream g and contain third
The liquid phase stream h of alkene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into first part logistics i and second part logistics j, first
Divide logistics i as the three logistics b of cyclic carbon；Second part logistics j return to depropanizing tower, first part's logistics i with
The flow-rate ratio of second part logistics j is 0.01-2:1；
Wherein, in step (2), hydrogenation material obtained by step (1), which is carried out gas-liquid separation, includes:
1) gained hydrogenation material is subjected to pre-separation in selective hydrogenation reaction device and obtains gaseous stream e and liquid phase stream f；
2) it the gaseous stream e and liquid phase stream f is introduced into knockout drum respectively carries out gas-liquid separation and obtain described containing third
Alkene, the gaseous stream g of propane and the liquid phase stream h containing propylene, propane.
2. according to the method described in claim 1, wherein, the selective hydrogenation reaction device includes that the selection positioned at middle and upper part adds hydrogen
Catalyst bed, the pre-separation tank positioned at selective hydrogenation reaction device middle and lower part, the liquid phase object positioned at selective hydrogenation reaction device bottom
The outlet f is flowed, the outlet gaseous stream e and top feed mouth positioned at middle and lower part, wherein will be from the depropanizing tower of propylene production technology
The fresh C3 fraction a containing propine and/or allene of extraction, after cyclic carbon three logistics b and hydrogen c mixing from the top
Feed inlet carries out the pre-separation into after contacting with the selective hydrogenation catalyst bed, into gas-liquid pre-separation tank.
3. according to the method described in claim 1, wherein, the gaseous stream e and liquid phase stream f distinguish without subcooler
It is introduced into knockout drum and carries out gas-liquid separation.
4. according to the method described in claim 1, wherein, first part's logistics i is returned as the three logistics b of cyclic carbon
It is directly mixed with fresh C3 fraction a when to selective hydrogenation reaction device without supercooling.
5. method described in any one of -4 according to claim 1, wherein the fresh C3 fraction a, which is needed not move through, to be added
Hot device improves temperature.
6. according to the method described in claim 1, wherein, step (1) the three logistics b of cyclic carbon and fresh C3 fraction a's
Flow-rate ratio is 0.2-0.8:1.
7. according to the method described in claim 1, wherein, the flow-rate ratio of step (3) the logistics i and logistics j are 0.2-1:1.
8. according to the method described in claim 1, wherein, the gaseous stream g containing propylene, propane that gas-liquid separation obtains is drawn
To subsequent propylene rectifying column, the pressure of the selective hydrogenation reaction device is by being drawn out to the gaseous stream g of subsequent propylene rectifying column
Flow adjust.
9. method described in any one of -4 according to claim 1, wherein the selection hydroconversion condition includes: hydrogen alkynes mole
Than for 0.5-2, reaction pressure 1-4MPa, inlet temperature is 5-50 DEG C, outlet temperature is 20-80 DEG C, propine in gaseous stream g
And/or the molar content of allene is 0-500ppm.
10. method described in any one of -4 according to claim 1, wherein the selective hydrogenation catalyst include carrier and
The main active component being supported on carrier, the carrier are selected from aluminium oxide, silica, titanium oxide, zinc oxide, molecular sieve, carbonization
One of silicon, calcium carbonate, kaolin and cordierite are a variety of, and the main active component element is in palladium, ruthenium and platinum element
At least one.
11. according to the method described in claim 10, wherein, the selective hydrogenation catalyst further includes being supported on helping on carrier
Active component, it is described that active component element is helped to be selected from alkali metal element, alkali earth metal, transition metal element, rare earth element
With one of V A race metallic element or a variety of.
12. according to the method for claim 11, wherein it is described help active component element be selected from silver, copper, zinc, potassium, sodium, magnesium,
One of calcium, beryllium, tin, lead, cadmium, strontium, barium, radium, manganese, zirconium, molybdenum and Germanium are a variety of.
13. method according to claim 11 or 12, wherein on the basis of the total amount of selective hydrogenation catalyst, with element
Meter, the content of the main active component are 0.01-1 weight %, and the content for helping active component is 0.01-2 weight %.
14. according to the method for claim 13, wherein the content of the main active component is 0.01-0.5 weight %, institute
Stating and helping the content of active component is 0.01-1 weight %.
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| CN106608786B (en) * | 2015-10-22 | 2019-06-11 | 中国石油化工股份有限公司 | The method of alcohol ether dimethylbenzene coproduction ethylbenzene |
| CN111205156A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Selective liquid phase hydrogenation method for carbon three fraction |
| CN111205153B (en) * | 2018-11-22 | 2022-11-18 | 中国石油化工股份有限公司 | Carbon three-fraction liquid-phase hydrogenation reaction device and method |
| CN111203168A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Jet loop reactor and method for selective liquid phase hydrogenation of carbon three-fraction |
| CN113741565A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Automatic control method and system for double-section bed carbon three-liquid phase hydrogenation reactor |
| CN115403438B (en) * | 2021-05-26 | 2024-03-26 | 中国石油化工股份有限公司 | Automatic control method and automatic control system for carbon three-liquid-phase hydrogenation reactor |
| CN114100542B (en) * | 2021-11-26 | 2022-08-16 | 北京恒泰洁能科技有限公司 | Energy expansion reconstruction device and method for cracking gas front hydrogenation device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762956A (en) * | 1983-04-13 | 1988-08-09 | Beijing Research Institute Of Chemical Industry He Ping Li | Novel catalyst and process for hydrogenation of unsaturated hydrocarbons |
| US4940687A (en) * | 1983-04-13 | 1990-07-10 | Beijing Research Institute Of Chemical Industry | Catalyst and process for hydrogenation of unsaturated hydrocarbons |
| WO1994004477A1 (en) * | 1992-08-24 | 1994-03-03 | Chemical Research & Licensing Company | Selective hydrogenation of dienes and acetylenes in c3 streams |
| CN1418180A (en) * | 2000-03-24 | 2003-05-14 | 催化蒸馏技术公司 | Process for removal of mapd from hydrocarbon streams |
| CN101139242B (en) * | 2006-09-07 | 2011-05-04 | 中国石油化工股份有限公司 | Method for liquid phase selective hydrogenation of C3 hydrocarbons |
| CN102249836A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Selective hydrogenation method for allylene and allene in propylene material flow |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7402720B2 (en) * | 2002-12-19 | 2008-07-22 | Exxonmobil Chemical Patents Inc. | Distillation process for removal of methyl acetylene and/or propadiene from an olefin stream |
| US20060084830A1 (en) * | 2004-10-20 | 2006-04-20 | Catalytic Distillation Technologies | Selective hydrogenation process and catalyst |
-
2015
- 2015-10-23 CN CN201510696786.XA patent/CN106608805B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762956A (en) * | 1983-04-13 | 1988-08-09 | Beijing Research Institute Of Chemical Industry He Ping Li | Novel catalyst and process for hydrogenation of unsaturated hydrocarbons |
| US4940687A (en) * | 1983-04-13 | 1990-07-10 | Beijing Research Institute Of Chemical Industry | Catalyst and process for hydrogenation of unsaturated hydrocarbons |
| WO1994004477A1 (en) * | 1992-08-24 | 1994-03-03 | Chemical Research & Licensing Company | Selective hydrogenation of dienes and acetylenes in c3 streams |
| CN1418180A (en) * | 2000-03-24 | 2003-05-14 | 催化蒸馏技术公司 | Process for removal of mapd from hydrocarbon streams |
| CN101139242B (en) * | 2006-09-07 | 2011-05-04 | 中国石油化工股份有限公司 | Method for liquid phase selective hydrogenation of C3 hydrocarbons |
| CN102249836A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Selective hydrogenation method for allylene and allene in propylene material flow |
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