CN106608805A - C3 fraction liquid phase selective hydrogenation method - Google Patents
C3 fraction liquid phase selective hydrogenation method Download PDFInfo
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- CN106608805A CN106608805A CN201510696786.XA CN201510696786A CN106608805A CN 106608805 A CN106608805 A CN 106608805A CN 201510696786 A CN201510696786 A CN 201510696786A CN 106608805 A CN106608805 A CN 106608805A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- 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 C3 fraction liquid phase selective hydrogenation method, wherein the method comprises the steps: mixing propargyl and/or allene-containing fresh C3 fraction a extracted from a depropanization tower in a propylene production process, a circular C3 material flow b and hydrogen gas c, then making the mixture contact with a selective hydrogenation catalyst, and carrying out selective hydrogenation; carrying out gas-liquid separation of the material obtained from the selective hydrogenation to obtain a gas phase material flow g containing propylene and propane and a liquid phase material flow h containing propylene and propane; dividing the liquid phase material flow h containing propylene and propane into a first part material flow i and a second part material flow j, and taking the first part material flow i as the circular C3 material flow b; and allowing the second part material flow j to return to the depropanization tower. The method provided by the invention not only effectively removes acetylene and/or allene in the C3 fraction but also reduces the energy consumption, and has incomparable superiority compared with the prior art.
Description
Technical field
The present invention relates to a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons.
Background technology
Petroleum hydrocarbon steam cracking is to prepare the most important method of the olefin monomers such as propylene.Production of propylene mistake
The alkynes and alkadienes produced in journey is the objectionable impurities for affecting propylene polymerization, and they can suppress propylene
The activity of polymerization catalyst, increases the consumption of catalyst, reduces the property of acrylic polymers product, so
Must be removed.It is industrial generally to be removed in cracking gas using catalysis selective hydrogenation method and solvent absorption
Alkynes and alkadienes.The technological process of catalysis selective hydrogenation method is simple, and Propylene Selectivity is high, and by-pass product is few,
It is the prefered method of green chemistry process, using more prevalent without environmental pollution.
US4571442A (1986) discloses a kind of acetylene liquid phase selective hydrogenation technique, will contain acetylene and ethene
Cut to be hydrogenated be dissolved in a kind of compositions of hydrocarbons diluent, then by formed liquid together with hydrogen
Hydrogenation reactor is sent into, in the reactor from the top down by the catalyst bed of supported palladium on an aluminum oxide
Layer carries out liquid phase selective hydrogenation.The gas-liquid mixture for being obtained sends into flash tank Jing after heat exchanger cooling,
Purified gas cut is separated with liquid diluent in flash tank.Liquid diluent after separation can be followed
Ring is used.Liquid diluent includes at least one aromatic hydrocarbons and at least one selected from primary amine, secondary amine and polynary
The amines of amine.
GB1175709A (1969) is disclosed and a kind of set into the liquid phase catalytic hydrogenation of hexamethylene for benzene hydrogenation
It is standby.In the liquid catalyst hydrogenation plant, hydrogen and liquid introduce hydrogenation reactor, by reactor
The beds and orifice plate in portion, gas phase is separated in the gas phase separation chamber in portion in the reactor, is passed through
Pipeline discharges reactor, and liquid phase continues through the beds and orifice plate of reactor lower part, and reverse
The hydrogen contact of flowing, the liquid after hydrogenation flows out from reactor bottom.The gas discharged by gas phase phase separation chamber
Body, sequentially passes through by cooler after two heat exchangers, and the liquid component gasified in mixture is in cooler
In be condensed into liquid, produce biphase gas and liquid flow, enter back into separator.In the separator, gas phase and liquid
It is separated.
CN101139242B discloses a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons.Containing propine and/
Or after the C3 fraction of allene mixes with hydrogen, the mixture for being obtained is by selective hydrogenation reaction device top
Into from top to bottom by the selective hydrogenation catalyst bed in reactor, connecing with selective hydrogenation catalyst
Touch.Hot discharging (liquids and gases mixture) from the extraction of selective hydrogenation reaction device bottom is without heat exchange
Device and/or cooler are cooled down, and being directly entered knockout drum carries out gas-liquid separation.Gas phase portion enters one
The condenser of knockout drum top or top is placed in, and draws condensed liquid and entered as product
Subsequent processing, the emptying of uncooled gas phase or is sent to fuel gas pipe network or is sent to two sections of compressor, three sections
Or four sections of entrances, adjust selection by controlling the gas phase flow rate of the temperature in condenser and/or control emptying
Pressure in hydrogenation reactor.A part from knockout drum liquid material out and fresh carbon
After the mixing of three cuts, together into hydrogenation reactor, another part is 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
The fresh C3 fraction containing propine and allene of depropanization overhead extraction, Jing matches somebody with somebody hydrogen, adds into selection
Hydrogen reactor, hydrogenation reactor passes through from the top down built with the liquid phase selective hydrogenation catalyst of carbon three, charging
Selective hydrogenation catalyst bed, the liquid discharging of selective hydrogenation reaction device bottom needs Jing coolers to reduce temperature
Degree, the liquid after cooling carries out the separation of gas phase and liquid phase into knockout drum, gas phase emptying after separation
Or be sent to fuel gas pipe network or be sent to two sections, three sections or four sections entrances of compressor, a part of liquid phase stream
Recycle, mix with fresh C3 fraction；Another part liquid phase stream is sent to third as product output
Alkene rectifying column is refined.Traditional handicraft (or is put generally by knockout drum gas phase air compensation is adjusted
Sky amount) adjusting the pressure in hydrogenation reactor.
Existing liquid phase selective hydrogenation of C 3 hydrocarbons beds generally need using one section, two sections or
Three sections of serial or parallel connection arrangements, this hydrogenation reactor complex structure, and can only be by reactor feed
Propine and/or allene be removed within 1000ppm.The removing degree of this propine and/or allene
Most of factories are all difficult to receive, factory generally requires and for propine and/or allene to be removed to 200ppm
Below.
The content of the invention
Can not effectively remove in C3 fraction for the method for prior art liquid phase selective hydrogenation of C 3 hydrocarbons
Propine and/or the big defect of allene, liquid phase selective hydrogenation of C 3 hydrocarbons complex procedures and energy consumption, this
It is bright that a kind of method of new liquid phase selective hydrogenation of C 3 hydrocarbons is provided.Method provided by the present invention, not only
Simplify liquid phase selective hydrogenation of C 3 hydrocarbons operation, reduce energy consumption of reaction, and improve propine and/
Or the removal effect of allene.
The present invention provides a kind of method of new liquid phase selective hydrogenation of C 3 hydrocarbons, and the method includes following step
Suddenly：
(1) will produce from the depropanizing tower of propylene production technology fresh containing propine and/or allene
After C3 fraction a, logistics b of cyclic carbon three and hydrogen c mixing in the case where hydroconversion condition is selected, selecting to add
Contacting with selective hydrogenation catalyst in hydrogen reactor carries out selection hydrogenation；
(2) step (1) gained hydrogenation material is carried out into gas-liquid separation, is obtained containing propylene, propane
The gaseous stream g and liquid phase stream h containing propylene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into into Part I logistics i and second
Fraction of stream j, Part I logistics i is used as logistics b of the cyclic carbon three；Part II logistics j is returned
To depropanizing tower.
The method that the present invention is provided is simplifying liquid phase selective hydrogenation of C 3 hydrocarbons operation, reduces reaction energy
While consumption, the removal effect of propine and/or allene is improved.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
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
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons, the method includes following step
Suddenly：
(1) will produce from the depropanizing tower of propylene production technology fresh containing propine and/or allene
After C3 fraction a, logistics b of cyclic carbon three and hydrogen c mixing in the case where hydroconversion condition is selected, selecting to add
Contacting with selective hydrogenation catalyst in hydrogen reactor carries out selection hydrogenation；
(2) step (1) gained hydrogenation material is carried out into gas-liquid separation, is obtained containing propylene, propane
The gaseous stream g and liquid phase stream h containing propylene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into into Part I logistics i and second
Fraction of stream j, Part I logistics i is used as logistics b of the cyclic carbon three；Part II logistics j is returned
To depropanizing tower.
In the present invention, preferably first will produce from the depropanizing tower of propylene production technology in step (1)
After the completion of fresh C3 fraction a and logistics b of cyclic carbon three mixing containing propine and/or allene, with hydrogen
Gas c mixes.
In accordance with the present invention it is preferred that, the fresh C3 fraction a is by order during production of propylene
Depropanization overhead extraction in separation process containing propylene, propane, propine and/or allene, it is also possible to
C3 fraction containing a small amount of cyclopropane, the component of a small amount of carbon more than four.
In accordance with the present invention it is preferred that, propine and/or allene mole contains in the fresh C3 fraction a
Measure as 0.2-8%.
In the present invention, step (1) gained hydrogenation material can be introduced directly into knockout drum is carried out
Gas-liquid separation, it is also possible to carry out step (1) gained hydrogenation material in selective hydrogenation reaction device first pre-
Gaseous stream and liquid phase stream are obtained after separation, and gaseous stream and liquid phase stream are introduced into respectively gas-liquid point
Gas-liquid separation is carried out from tank.
In accordance with the present invention it is preferred that, in step (2), step (1) gained hydrogenation material is entered into promoting the circulation of qi
Liquid is separated to be included：
1】Gained hydrogenation material is carried out into pre-separation in selective hydrogenation reaction device and obtains gaseous stream e and liquid
Phase logistics f；
2】The gaseous stream e and liquid phase stream f are introduced respectively into knockout drum carries out gas-liquid separation
Obtain the liquid phase stream h containing propylene, the gaseous stream g of propane and containing propylene, propane.
Compared with prior art, using this preferred embodiment, step (1) gained hydrogenation thing is enabled to
Material gas-liquid separation effect is more preferable.
In the present invention, the gaseous stream g can contain a small amount of propine and/or allene, also may be used
Not contain propine and allene.
In the present invention, the liquid phase stream h can contain a small amount of propine and/or allene, also may be used
Not contain propine and allene.
In accordance with the present invention it is preferred that, the selective hydrogenation reaction device includes that the selection for being located at middle and upper part is hydrogenated with
Beds, positioned at the pre-separation tank of selective hydrogenation reaction device middle and lower part, positioned at selective hydrogenation reaction device
The liquid phase stream f outlets of bottom, the gaseous stream e outlets and its top feed mouth positioned at middle and lower part, wherein,
By the fresh C3 fraction containing propine and/or allene produced from the depropanizing tower of propylene production technology
Enter from its top feed mouth after a, logistics b of cyclic carbon three and hydrogen c mixing and select hydrogenation with described
After beds contact, into gas-liquid pre-separation tank the pre-separation is carried out.
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
The gaseous stream e outlets of device middle and lower part are drawn, and the liquid phase stream f that pre-separation is obtained is from positioned at selection hydrogenation
The liquid phase stream f outlets of reactor bottom are drawn.
In accordance with the present invention it is preferred that, the gaseous stream e and liquid phase stream f, without subcooler,
Being introduced between knockout drum carries out gas-liquid separation.Using this preferred embodiment, ensureing technique effect
While, energy consumption is reduced, operate simpler.
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, Part I logistics i is returned as logistics b of the cyclic carbon three
Directly mix with fresh C3 fraction a without supercooling when returning to selective hydrogenation reaction device.
In accordance with the present invention it is preferred that, the fresh C3 fraction a needs not move through heater to improve temperature
Degree.
In the present invention, because the liquid phase stream of selective hydrogenation reaction device bottom discharge is directly entered gas-liquid point
From tank not through heat exchanging process, without cooling, so the liquid phase of selective hydrogenation reaction device bottom discharge
When a part of Jing gas-liquid separations Posterior circle in logistics is to selective hydrogenation reaction device entrance, select for improving
The fresh C3 fraction a temperature of hydrogenation reactor entrance can heating load it is more, therefore, people in the art
Member can be by adjusting logistics b of cyclic carbon three with the flow-rate ratio of fresh C3 fraction a come control selections hydrogenation
The temperature of reactor inlet C3 fraction.
As needed, if the shortage of heat of logistics b of cyclic carbon three offer, it is also possible to by heater pair
Material into selective hydrogenation reaction device is heated.The method provided using the present invention substantially increases carbon
The flexibility of three cut liquid phase selective hydrogenations operation.
In accordance with the present invention it is preferred that, step (1) cyclic carbon three logistics b and fresh C3 fraction a
Flow-rate ratio be 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 by step (3)
Fraction of stream i and Part II logistics j, Part I logistics i is used as logistics b of the cyclic carbon three；The
Two fraction of stream j return to depropanizing tower.
Part I logistics i is entered through being pumped into selective hydrogenation reaction device entrance with diluting reactor entrance
The content of propine and/or allene in material, adjusting the flow of Part I logistics i can be added with control selections
The flow and temperature of hydrogen reactor inlet feed.
Part II logistics j returns to depropanizing tower, can reduce depropanizing tower charging in propine and/
Or the concentration of allene, moreover it is possible to increase the separating effect of depropanizing tower, reducing energy consumption.
The present invention is by regulation liquid phase stream h between Part I logistics i and Part II logistics j
Distribution such that it is able to more flexibly adjust the logistics flux of carbon three, the temperature of selective hydrogenation reaction device entrance
With propine and/or the content of allene, it is more beneficial for removing the propine and/or allene in C3 fraction.
In the present invention, those skilled in the art can be by specifically needing logistics i described to step (3)
Be adjusted with the flow-rate ratio of logistics j, with the flow of the selective hydrogenation reaction device entrance required for obtaining,
The content of temperature and propine and/or allene.
It should be noted that the larger fluctuation of the flow of Part II logistics j should be avoided, in order to avoid cause
The excessive operation fluctuation of depropanizing tower.
In accordance with the present invention it is preferred that, step (3) logistics i is 0.01-2 with the flow-rate ratio of logistics j：
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
It is drawn out to subsequent propylene rectifying column further to process.
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
The flow of the gaseous stream g of rectifying column is adjusting.
In the present invention, for the hydroconversion condition that selects in selective hydrogenation reaction device does not have special restriction,
It can be the conventional selection hydroconversion condition in this area, it is preferable that the selection in the selective hydrogenation reaction device
Hydroconversion condition includes：The hydrogen alkynes mol ratio (mol ratio of propine and/or allene i.e. in hydrogen and C3 fraction
Value) it is 0.5-2, reaction pressure is 1-4MPa, and inlet temperature is 5-50 DEG C, outlet temperature is 20-80 DEG C,
The molar content of propine and/or allene is 0-500ppm in gaseous stream g.
In the present invention, the selective hydrogenation catalyst can be used for C3 fraction liquid for this area is any
Mutually select the catalyst of hydrogenation.
Preferably, the selective hydrogenation catalyst includes carrier and the main active component being supported on carrier,
The support selected from alumina, silica, titanium oxide, zinc oxide, molecular sieve, carborundum, calcium carbonate,
One or more in kaolin and cordierite, the main active component element is selected from palladium, ruthenium and platinum element
In at least one.
Preferably, the selective hydrogenation catalyst also includes the active component that helps being supported on carrier, described
Active component element is helped to be selected from alkali metal, alkali earth metal, transition metal, rare earth element
With one or more in VA races metallic elements, preferably silver, copper, zinc, potassium, sodium, magnesium, calcium,
One or more in beryllium, tin, lead, cadmium, strontium, barium, radium, manganese, zirconium, molybdenum and Ge element.
In accordance with the present invention it is preferred that, on the basis of the total amount of selective hydrogenation catalyst, in terms of element, institute
The content for stating main active component is 0.01-1 weight %, and preferably 0.01-0.5 weight % is described to help activity
The content of component is 0.01-2 weight %, preferably 0.01-1 weight %.
Compared with the method for traditional liquid phase selective hydrogenation of C 3 hydrocarbons, the C3 fraction liquid phase choosing of the present invention
Selecting the method advantage of hydrogenation can be summarized as follows：
1st, in traditional liquid phase selective hydrogenation of C 3 hydrocarbons technique, selective hydrogenation reaction device bottom discharge Jing
Subcooler is cooled down, and entering back into knockout drum carries out gas-liquid two-phase separation.First carry out due to discharging cold
But, the liquid material of extraction is partly into after subsequent propylene rectifying column and also need heating, another part circulation
To selective hydrogenation reaction device entrance liquid material improve entrance fresh material temperature can heating load it is less,
Thus energy utilization is unreasonable, energy consumption is larger, and operation difficulty is larger.The C3 fraction liquid that the present invention is provided
In mutually selecting the technique of hydrogenation, the discharging of selective hydrogenation reaction device Base Heat into knockout drum it
Before, using special liquid phase, gas phase difference discharge method, it is ensured that the selective hydrogenation reaction device of carbon three is in
Trickle bed operational mode, keeps selective hydrogenation reaction device constant by the gasification of carbon 3 material in course of reaction
Outlet temperature, by the discharging of sidepiece gas phase ensureing liquid level not superelevation, prevent catalyst to be submerged.By
In the liquid of selective hydrogenation reaction device bottom discharge knockout drum is directly entered not through heat exchange
Journey, without cooling, so a part of Jing gas-liquid separations in the liquid of selective hydrogenation reaction device bottom discharge
When Posterior circle is to selective hydrogenation reaction device entrance, for improving selective hydrogenation reaction device entrance delivered fresh material temperature
Degree can heating load it is more.Therefore, the method for the present invention simplifies conventional process flow, and energy consumption is low, behaviour
Make convenient.
2nd, in traditional liquid phase selective hydrogenation of C 3 hydrocarbons technique, by the way of knockout drum tonifying Qi
The pressure of selective hydrogenation reaction device is adjusted, typically tonifying Qi is carried out using hydrogen, so sometimes resulted in excessive
Bringing into for hydrogen, is unfavorable for follow-up propylene distillation operation.The method of the present invention is drawn by directly regulation
Go out the flow to the gaseous stream g of subsequent propylene rectifying column to adjust the pressure of selective hydrogenation reaction device, carry
The controllability of high C3 fraction selective hydrogenation reaction in liquid phase process.
3rd, traditional C 3 fraction selective hydrogenation process adjustments means are few, particularly work as selective hydrogenation reaction
It is still anti-without can effectively dilute selection hydrogenation at present when the propine and/or higher allene content of device entrance
Answer device entrance propine and/or allene content to ensure suitably to export propine and/or allene content requirement
Measure.The present invention by adjust liquid phase stream h Part I logistics i and Part II logistics j it
Between distribution such that it is able to the more flexible thing of carbon three adjusted into the selective hydrogenation reaction device entrance of carbon three
Stream flow, the content of temperature and propine and/or allene, the propine for being more beneficial for removing in C3 fraction and
/ or allene.
4th, the present invention provide method can with replace prior art to be adopted with single hop bed hydroprocessing mode one
Section, two sections, the mode of three sections of serial or parallel connections hydrogenation, the method that the present invention is provided is cracked with conventional hydrocarbon-based
The liquid phase selective hydrogenation method of carbon three in technique compares, low equipment investment more reasonable with energy utilization,
The advantages of product quality is controllable.
The implementation process and produced beneficial effect of the present invention are described in detail below by way of specific embodiment,
The Spirit Essence for being intended to help reader to more clearly understand the present invention is located, but can not be to the reality of the present invention
Apply scope and constitute any restriction.
Embodiment 1
According to the flow process of the liquid phase selective hydrogenation of carbon three of the invention shown in Fig. 1.
Obtained by carbon 3 material f0 is reacted in depropanizing tower S0 by depropanizing tower S0 overhead extractions
Material f1 Jing pump S1 pass sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (flow is 180t/h, propine and the third two
The molar content sum of alkene for 3%), logistics b of cyclic carbon three (flow is 90t/h) mixing after, with hydrogen
C mixing (hydrogen flowing quantity is 380kg/h, and hydrogen purity is 95%, and other impurity are methane) Jing S3 are changed
After heat, the mixture d for being obtained enters reactor by selective hydrogenation reaction device top, passes through from top to bottom
Selective hydrogenation catalyst bed R1 in selective hydrogenation reaction device, with the liquid phase selective hydrogenation catalyst of carbon three
Contact (BC-L-83 that catalyst is provided for sinopec Beijing Chemical Research Institute), reactor pressure is
2.40MPa, reactor inlet temperature is 38 DEG C, and reactor outlet temperature is 60 DEG C.
Pre-separation tank after carrying out selective hydrogenation reaction, by gained hydrogenation material in selective hydrogenation reaction device
Pre-separation is carried out in S4 and obtains gaseous stream e and liquid phase stream f, by gaseous stream e by selecting hydrogenation
The middle and upper part of reactor, liquid phase stream f are drawn out to respectively gas-liquid point by the bottom of selective hydrogenation reaction device
Gas-liquid two-phase separation is carried out from tank S5, knockout drum S5 pressure is 2.40MPa.Knockout drum
S5 and reboiler S6 are shared, and (propine and allene molar content are less than the gaseous stream g for obtaining
Propylene rectification tower 200ppm) is entered, the flow of gaseous stream g is 90t/h, and by adjusting propylene is entered
The flow of the gaseous stream g of rectifying column adjusts the pressure of selective hydrogenation reaction device to 2.4MPa；Obtain
Liquid material h in Part I logistics i as logistics b of cyclic carbon three (flow is 90t/h) Jing pumps
S7 conveyings are mixed into selective hydrogenation reaction device, the liquids that gas-liquid separation is obtained with fresh C3 fraction a
Part II logistics j in material h returns to depropanizing tower S0, and the flow of liquid phase stream j is 100t/h.
The method provided using the present embodiment, is simplifying liquid phase selective hydrogenation of C 3 hydrocarbons operation, drop
While low energy consumption so that propine and allene molar content in gained gaseous stream g after gas-liquid separation
Less than 200ppm.
Comparative example l
According to the flow process of the traditional liquid phase selective hydrogenation of carbon three shown in Fig. 2.
Obtained by carbon 3 material f0 is reacted in depropanizing tower S0 by depropanizing tower S0 overhead extractions
Material f1 Jing pump S1 pass 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%, flow is 180t/h) mix with hydrogen c, hydrogen flowing quantity is 380kg/h, and hydrogen purity is 95%,
The mixture d for being obtained enters selective hydrogenation reaction device by selective hydrogenation reaction device R1 tops, from up to
Down by the selective hydrogenation catalyst bed in reactor, contact with the liquid phase selective hydrogenation catalyst of carbon three
(sinopec Beijing Chemical Research Institute provide BC-L-83), reactor pressure is 2.40MPa, reactor
Inlet temperature is 38 DEG C, and reactor outlet temperature is 60 DEG C.
After carrying out selective hydrogenation reaction, selective hydrogenation reaction device R1 bottom discharge m are introduced into a cooling
Device S9 is cooled down, and entering back into a knockout drum S5 carries out gas-liquid two-phase separation, knockout drum
S5 pressure is 2.40MPa.Gaseous stream g emptying after gas-liquid separation, from knockout drum S5 out
Liquid stream h in a part of i convey as the recycle stock Jing pumps S7 of carbon three, Jing heat exchanger S8 change
Reactor is mixed into fresh C3 fraction a after heat, the circular flow of carbon three is 90t/h；Another part
N is sent to propylene rectification tower and is refined as product, and the flow of liquid phase stream n is 100t/h, liquid phase thing
The molar content of propine and allene is about 1000ppm in stream n.
Embodiment 2
According to the method described in embodiment 1, except for the difference that the flow of fresh C3 fraction a is 210t/h,
The flow of logistics b of cyclic carbon three is 100t/h, and the flow of gaseous stream g is 110t/h, accordingly, is led to
Overregulate flow into the gaseous stream g of propylene rectification tower by the pressure of selective hydrogenation reaction device adjust to
2.35MPa。
The method provided using the present embodiment so that after gas-liquid separation gained gaseous stream g in propine and
Allene molar content is less than 200ppm.
Embodiment 3
According to the flow process of the liquid phase selective hydrogenation of carbon three of the invention shown in Fig. 1.
Obtained by carbon 3 material f0 is reacted in depropanizing tower S0 by depropanizing tower S0 overhead extractions
Material f1 Jing pump S1 pass sequentially through water drier S2 and dearsenification reactor R2.
By the fresh C3 fraction a produced from dearsenification reactor R2, (flow is 150t/h, propine and the third two
The molar content sum of alkene for 2.5%), logistics b of cyclic carbon three (flow is 75t/h) mixing after, with hydrogen
Gas c mixing (hydrogen flowing quantity is 290kg/h, and hydrogen purity is 95%, and other impurity are methane) Jing S3
After heat exchange, the mixture d for being obtained enters reactor by selective hydrogenation reaction device top, leads to from top to bottom
The selective hydrogenation catalyst bed R1 crossed in selective hydrogenation reaction device, with the catalysis of the liquid phase selective hydrogenation of carbon three
Agent contacts (BC-L-83 that catalyst is provided for sinopec Beijing Chemical Research Institute), and reactor pressure is
2.35MPa, reactor inlet temperature is 40 DEG C, and reactor outlet temperature is 58 DEG C.
Pre-separation tank after carrying out selective hydrogenation reaction, by gained hydrogenation material in selective hydrogenation reaction device
Pre-separation is carried out in S4 and obtains gaseous stream e and liquid phase stream f, by gaseous stream e by selecting hydrogenation
The middle and upper part of reactor R1, liquid phase stream f are drawn out to respectively by the bottom of selective hydrogenation reaction device R1
Knockout drum S5 carries out gas-liquid two-phase separation, and knockout drum S5 pressure is 2.35MPa.Gas-liquid point
Share from tank S5 and reboiler S6, (propine and allene molar content are less than the gaseous stream g for obtaining
Propylene rectification tower 100ppm) is entered, the flow of gaseous stream g is 80t/h, and by adjusting propylene is entered
The flow of the gaseous stream g of rectifying column adjusts the pressure of selective hydrogenation reaction device to 2.35MPa；Obtain
Liquid material h in Part I logistics i as logistics b of cyclic carbon three (flow is 75t/h) Jing pumps
S7 conveyings are mixed into selective hydrogenation reaction device, the liquids that gas-liquid separation is obtained with fresh C3 fraction a
Part II logistics j in material h returns to depropanizing tower S0, and the flow of liquid phase stream j is 80t/h.
The method provided using the present embodiment so that after gas-liquid separation gained gaseous stream g in propine and
Allene molar content is less than 100ppm.
Comparative example 2
According to the flow process of the traditional liquid phase selective hydrogenation of carbon three shown in Fig. 2.
Obtained by carbon 3 material f0 is reacted in depropanizing tower S0 by depropanizing tower S0 overhead extractions
Material f1 Jing pump S1 pass 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 is 150t/h) mix with hydrogen c, hydrogen flowing quantity is 290kg/h, and hydrogen purity is 95%,
The mixture d for being obtained enters selective hydrogenation reaction device by selective hydrogenation reaction device R1 tops, from up to
Down by the selective hydrogenation catalyst bed in reactor, contact with the liquid phase selective hydrogenation catalyst of carbon three
(sinopec Beijing Chemical Research Institute provide BC-L-83), reactor pressure is 2.35MPa, reactor
Inlet temperature is 40 DEG C, and reactor outlet temperature is 58 DEG C.
After carrying out selective hydrogenation reaction, selective hydrogenation reaction device R1 bottom discharge m are introduced into a cooling
Device S9 is cooled down, and entering back into a knockout drum S5 carries out gas-liquid two-phase separation, knockout drum
S5 pressure is 2.35MPa.Gaseous stream g emptying after gas-liquid separation, from knockout drum S5 out
Liquid stream h in a part of i convey as the recycle stock Jing pumps S7 of carbon three, Jing heat exchanger S8 change
Reactor is mixed into fresh C3 fraction a after heat, the circular flow of carbon three is 75t/h；Another part
N is sent to propylene rectification tower and is refined as product, and the flow of liquid phase stream n is 80t/h, liquid phase stream
The molar content of propine and allene is about 500ppm in n.
Embodiment 1 and comparative example 1, embodiment 3 and comparative example 2 are compared as can be seen that the present invention is carried
For liquid phase selective hydrogenation of C 3 hydrocarbons method be not only effectively stripped of propine and/or third in C3 fraction
Diene, while energy consumption is reduced, with the superiority that prior art is incomparable.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons, the method is comprised the following steps：
(1) will produce from the depropanizing tower of propylene production technology fresh containing propine and/or allene
After C3 fraction a, logistics b of cyclic carbon three and hydrogen c mixing in the case where hydroconversion condition is selected, selecting to add
Contacting with selective hydrogenation catalyst in hydrogen reactor carries out selection hydrogenation；
(2) step (1) gained hydrogenation material is carried out into gas-liquid separation, is obtained containing propylene, propane
The gaseous stream g and liquid phase stream h containing propylene, propane；
(3) the liquid phase stream h containing propylene, propane is divided into into Part I logistics i and second
Fraction of stream j, Part I logistics i is used as logistics b of the cyclic carbon three；Part II logistics j is returned
To depropanizing tower.
2. method according to claim 1, wherein, in step (2), by step (1) institute
Hydrogenation material carries out gas-liquid separation and includes：
1】Gained hydrogenation material is carried out into pre-separation in selective hydrogenation reaction device and obtains gaseous stream e and liquid
Phase logistics f；
2】The gaseous stream e and liquid phase stream f are introduced respectively into knockout drum carries out gas-liquid separation
Obtain the liquid phase stream h containing propylene, the gaseous stream g of propane and containing propylene, propane.
3. method according to claim 2, wherein, the selective hydrogenation reaction device includes being located at
The selective hydrogenation catalyst bed of middle and upper part, positioned at the pre-separation tank of selective hydrogenation reaction device middle and lower part, position
In selective hydrogenation reaction device bottom liquid phase stream f export, positioned at middle and lower part gaseous stream e outlet and
Its top feed mouth, wherein, will produce from the depropanizing tower of propylene production technology containing propine and/or the third two
Enter from its top feed mouth after the fresh C3 fraction a of alkene, logistics b of cyclic carbon three and hydrogen c mixing
Enter after contacting with the selective hydrogenation catalyst bed, into gas-liquid pre-separation tank the pre-separation is carried out.
4. according to the method in claim 2 or 3, wherein, the gaseous stream e and liquid phase thing
Stream f, without subcooler, being introduced between knockout drum carries out gas-liquid separation.
5. method according to claim 1, wherein, Part I logistics i is used as described
When logistics b of cyclic carbon three returns to selective hydrogenation reaction device without supercooling directly and fresh C3 fraction a
Mixing.
6. the method according to any one in claim 1-5, wherein, the fresh carbon three evaporates
A is divided to need not move through heater to improve temperature.
7. method according to claim 1, wherein, logistics b of step (1) cyclic carbon three
It is 0.01-1 with the flow-rate ratio of fresh C3 fraction a：1, preferably 0.2-0.8：1.
8. method according to claim 1, wherein, step (3) logistics i and logistics j
Flow-rate ratio be 0.01-2：1, preferably 0.2-1：1.
9. method according to claim 1, wherein, gas-liquid separation obtain containing propylene, third
The gaseous stream g of alkane is drawn out to subsequent propylene rectifying column, and the pressure of the selective hydrogenation reaction device is by drawing
Go out the flow to the gaseous stream g of subsequent propylene rectifying column to adjust.
10. the method according to any one in claim 1-9, wherein, it is described to select hydrogenation bar
Part includes：Hydrogen alkynes mol ratio is 0.5-2, and reaction pressure is 1-4MPa, and inlet temperature is 5-50 DEG C, is gone out
Mouth temperature is 20-80 DEG C, and the molar content of propine and/or allene is 0-500ppm in gaseous stream g.
11. methods according to any one in claim 1-10, wherein, it is described to select hydrogenation
Catalyst includes carrier and the main active component being supported on carrier, the support selected from alumina, oxidation
One kind in silicon, titanium oxide, zinc oxide, molecular sieve, carborundum, calcium carbonate, kaolin and cordierite
Or various, at least one of the main active component element in palladium, ruthenium and platinum element.
12. methods according to claim 11, wherein, the selective hydrogenation catalyst also includes
The active component that helps being supported on carrier, it is described to help active component element selected from alkali metal, alkaline earth gold
One or more in category element, transition metal, rare earth element and VA races metallic element, it is excellent
Elect as silver, copper, zinc, potassium, sodium, magnesium, calcium, beryllium, tin, lead, cadmium, strontium, barium, radium, manganese, zirconium,
One or more in molybdenum and Ge element.
13. methods according to claim 12, wherein, the total amount with selective hydrogenation catalyst is
Benchmark, in terms of element, the content of the main active component is 0.01-1 weight %, preferably 0.01-0.5
Weight %, the content for helping active component is 0.01-2 weight %, preferably 0.01-1 weight %.
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| CN106608786A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for cooperatively producing ethylbenzene by preparing xylene from alcohol ether |
| 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 |
| 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 |
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| 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 |
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| 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 |
| 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 |
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| 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 |
| CN115407722A (en) * | 2021-05-27 | 2022-11-29 | 中国石油化工股份有限公司 | Automatic control method of carbon three-liquid-phase hydrogenation process system and carbon three-liquid-phase hydrogenation process system |
| CN115407722B (en) * | 2021-05-27 | 2024-10-15 | 中国石油化工股份有限公司 | Automatic control method of carbon three-liquid-phase hydrogenation process system and carbon three-liquid-phase hydrogenation process system |
| CN114100542A (en) * | 2021-11-26 | 2022-03-01 | 北京恒泰洁能科技有限公司 | Energy expansion reconstruction device and method for cracking gas front hydrogenation device |
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