CN107955642A - A kind of light dydrocarbon is raffinated oil and the method and system of coker gasoline mixed hydrogenation - Google Patents
A kind of light dydrocarbon is raffinated oil and the method and system of coker gasoline mixed hydrogenation Download PDFInfo
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- CN107955642A CN107955642A CN201610896074.7A CN201610896074A CN107955642A CN 107955642 A CN107955642 A CN 107955642A CN 201610896074 A CN201610896074 A CN 201610896074A CN 107955642 A CN107955642 A CN 107955642A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
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Abstract
The present invention relates to PETROLEUM PROCESSING field, and in particular, to a kind of light dydrocarbon is raffinated oil and the method for coker gasoline mixed hydrogenation and light dydrocarbon is raffinated oil and the system of coker gasoline mixed hydrogenation.The light dydrocarbon is raffinated oil and the method for coker gasoline mixed hydrogenation includes:Light dydrocarbon is raffinated oil and carries out pre-hydrotreating reaction so that the light dydrocarbon raffinate oil in diene hydrogenation saturation, carry out hydrogenation reaction jointly using the pre-hydrotreating reaction products therefrom as diluent and coker gasoline.The method and system of the present invention can efficiently solve coker gasoline and light dydrocarbon is raffinated oil during hydrogenation easy coking, the difficult point polymerizeing, and it can reasonably utilize resource, cost of material and energy loss are effectively reduced, and can effectively extend the cycle of operation of equipment.
Description
Technical field
The present invention relates to PETROLEUM PROCESSING field, and in particular, to a kind of light dydrocarbon is raffinated oil and coker gasoline mixed hydrogenation
Method and light dydrocarbon are raffinated oil and the system of coker gasoline mixed hydrogenation.
Background technology
Coker gasoline contains the alkene of high level, under independent hydroconversion condition, easily there is a situation where polymerization, coking,
Difficulty of processing is larger.
Ethylene side product light dydrocarbon is raffinated oil, the diolefin rich in high economic value, as light dydrocarbon comprehensive utilization technique, at present
C 5 diene subdivision has had more mature patented technology, and the hot issue of chemical research, its emphasis is by wherein
Chemical industry various useful monomers in short supply are separated, mainly alkadienes and iso-amylene, improve the comprehensive utilization rate of light dydrocarbon at present
Technology, be substantially using this thinking.But the ethene light dydrocarbon after the technology utilizes is raffinated oil still containing higher pair
Alkene, under Conventional processing conditions, easily polymerize, and produces the situation of coking, and processing and utilization difficulty is larger.
The content of the invention
The purpose of the present invention is overcome hydrotreating difficulty of the prior art for coker gasoline larger and/or the prior art
The larger deficiency of the hydrotreating difficulty raffinated oil to light dydrocarbon, there is provided a kind of light dydrocarbon is raffinated oil and the side of coker gasoline mixed hydrogenation
Method and light dydrocarbon are raffinated oil and the system of coker gasoline mixed hydrogenation.The method and system of the present invention can efficiently solve coking
Gasoline and light dydrocarbon are raffinated oil during hydrogenation easy coking, the difficult point of polymerization, and can reasonably utilize resource, effectively
Ground reduces cost of material and energy loss, and can effectively extend the cycle of operation of equipment.
In view of light dydrocarbon raffinate oil with coker gasoline exist " alkene of high concentration, alkene in hydrogenation reaction easily polymerization,
Coking, easily causes reactor and heat exchanger pressure difference to rise, coking and blocking heat exchanger causes device to be stopped work when serious " deficiency,
The inventors found that the hydrogenation reaction of light dydrocarbon can be raffinated oil hydrogenation reaction and coker gasoline dexterously combines,
It can be resolved with the above-mentioned deficiency of coker gasoline so as to which light dydrocarbon is raffinated oil, and can obtain that cracking of ethylene can be used as
The naphtha product and pumice product of raw material.Specifically, it was found by the inventors of the present invention that carrying out pre-add by the way that light dydrocarbon is raffinated oil
Hydrogen saturated process, thus the alkadienes during light dydrocarbon is raffinated oil carry out hydrogenation saturation and monoolefine do not occur hydrogenation reaction and
The reaction of desulfurization, denitrogenation does not occur, the product obtained by the pre- hydrogenation saturated process just may be used as Hydrogenation of Coker Gasoline reaction
Diluent so that effectively alleviate Hydrogenation of Coker Gasoline reaction coking the problem of, effectively extend system the cycle of operation.
First aspect present invention provides a kind of light dydrocarbon and raffinates oil and the method for coker gasoline mixed hydrogenation, wherein, the party
Method includes:By light dydrocarbon raffinate oil carry out pre-hydrotreating reaction so that the light dydrocarbon raffinate oil in diene hydrogenation saturation, will be described pre-
Hydrogenation reaction products therefrom carries out hydrogenation reaction jointly as diluent and coker gasoline.
Second aspect of the present invention provides a kind of light dydrocarbon and raffinates oil and the system of coker gasoline mixed hydrogenation, wherein, this is
System includes light dydrocarbon raffinate oil sources, coker gasoline source, pre-hydrogenator and hydrogenation reactor, the entrance of the pre-hydrogenator and
Light dydrocarbon raffinate oil sources connects, and the outlet of the pre-hydrogenator is connected with the entrance of hydrogenation reactor, the hydrogenation reactor
Entrance is also connected with coker gasoline source.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 that a kind of light dydrocarbon of embodiment is raffinated oil and coker gasoline mixed hydrogenation system according to the present invention.
Description of reference numerals
FI401 raw material dehydration devices;P205 is hydrogenated with feed pump in advance;The pre- hydrogenation heat exchangers of E271;E270 is hydrogenated with heater in advance;
R200 pre-hydrogenators;C202 circulating hydrogen compressors;The first hydrogenation heat exchangers of E201;The second hydrogenation heat exchangers of E202AB;
The 3rd hydrogenation heat exchangers of E202CD;F201 reaction heating furnaces;The first hydrogenation reactors of R201;The second hydrogenation reactors of R202;
V243 high pressure hot separators;V244 thermal low-pressure separators;V202 cold high pressure separators;V203 cold low separators;V206 dilutes
Agent storage tank;P204 diluent pumps;V201 feedstock oil surge tanks;P201 hydrogenating materials pump;T201 depriving hydrogen sulphide strippers;T203 is followed
Ring hydrogen desulfurizing tower;V204 recycle hydrogen liquid separation tanks.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
First aspect present invention provides a kind of light dydrocarbon and raffinates oil and the method for coker gasoline mixed hydrogenation, wherein, the party
Method includes:By light dydrocarbon raffinate oil carry out pre-hydrotreating reaction so that the light dydrocarbon raffinate oil in diene hydrogenation saturation, will be described pre-
Hydrogenation reaction products therefrom carries out hydrogenation reaction jointly as diluent and coker gasoline.
In the present invention, the situation of diene hydrogenation saturation of the pre-hydrotreating reaction in causing the light dydrocarbon to raffinate oil
Under want to that other reactions do not occur as far as possible, i.e., light dydrocarbons more than 90 weight % is raffinated oil, and that monoolefin hydrogenation does not occur is anti-
Should, desulphurization reaction or denitrification reaction and other reactions.In order to reach the purpose, the preferably bar by controlling pre-hydrotreating reaction
Part and realize.It was found by the inventors of the present invention that the temperature of pre-hydrotreating reaction ought be controlled below 150 DEG C, and catalyst is selected
When not containing the hydrogenation catalyst of heavy metal, above-mentioned purpose just can be realized.The temperature of the pre-hydrotreating reaction can be 100-
150 DEG C, be preferably 100-130 DEG C, more preferably 100-120 DEG C;Catalyst used in the pre-hydrotreating reaction can be various
The hydrogenation catalyst of heavy metal is not contained.
In the present invention, the condition of the pre-hydrotreating reaction further includes:Hydrogen-oil ratio can be 200-500v/v, be preferably
200-350v/v;Air speed can be 1.2-3.95h-1, it is preferably 1.6-3.95h-1;Pressure can be 3.5-5MPa, be preferably
3.8-5MPa。
In the present invention, the method further includes:Introduce additional diluent and the light dydrocarbon raffinates oil and carries out pre-add jointly
Hydrogen reacts, and there is no particular limitation for the dosage of the additional diluent, the use that the light dydrocarbon is raffinated oil with the additional diluent
The part by weight of amount such as can be 1:3-15, is preferably 1:5-10, more preferably 1:6-8.The species of the additional diluent does not have
There is special restriction, diluent commonly used in the art can be used, such as can be non-aromatic gasoline, that is, do not contain aromatic hydrocarbon
Gasoline;There is no particular limitation in the source of the additional diluent, for example, can be extracted by benzene, the mode such as Aromatics Extractive Project obtains
Arrive.
In the present invention, light dydrocarbon is raffinated oil wholly or largely diene hydrogenation therein by the pre-hydrotreating reaction
Saturation, it is preferable that light dydrocarbon raffinate oil carry out pre-hydrotreating obtained by material in alkadienes content reach 0.4 weight % with
Under, more preferably up to below 0.1 weight %.
In the present invention, light dydrocarbon is raffinated oil carry out the pre-hydrotreating after resulting material can act as diluent and coking
Gasoline carries out hydrogenation reaction jointly, so that the diene concentration in coker gasoline is diluted and then can effectively alleviate hydrogenation instead
Coking phenomenon during answering, makes hydrogenation reaction can trouble-free operation with long period.Therefore the pre-hydrotreating reaction products therefrom
It can be determined with the mixed proportion of coker gasoline according to the content of alkadienes in coker gasoline and the condition of hydrogenation reaction, example
Such as, the mixing ratio of the pre-hydrotreating reaction products therefrom and coker gasoline can be 1:1-2.5 it is preferably 1:1.5-2.
In the present invention, the light dydrocarbon is raffinated oil, the amount ratio of additional diluent and coker gasoline is according to recited above
The light dydrocarbon is raffinated oil and the amount ratio of the additional diluent and the pre-hydrotreating reaction products therefrom and coker gasoline
Mixing ratio determines, it is preferable that the light dydrocarbon is raffinated oil, the weight ratio of the dosage of additional diluent and coker gasoline while full
Foot 1:3-15:5-20, is preferably 1:5-10:8-16, is most preferably 1:6-8:12-16.
In the present invention, there is no particular limitation for the condition of the hydrogenation reaction, can be the hydrogenation bar of this area routine
Part, such as can include:Hydrogen-oil ratio is 250-600v/v, is preferably 350-500v/v;Air speed is 0.8-2h-1, it is preferably 0.8-
1.7h-1;Pressure is 3.5-4.5MPa, is preferably 3.8-4.5MPa;Temperature is 210-275 DEG C, is preferably 210-240 DEG C.
In the present invention, in order to more fully utilize system in material and the energy, it is preferable that the method further includes:
The hydrogenation reaction products therefrom is subjected to gas-liquid separation, by gained gas circulation return the pre-hydrotreating reaction and/or it is described plus
In hydrogen reaction.Normally, H in the gas obtained by the gas-liquid separation2Content about in 80 weight % or so, which can return
H is provided in the pre-hydrotreating reaction and/or the hydrogenation reaction2, further, since pre-hydrotreating reaction and hydrogenation reaction need to consume
H2, therefore, further need exist for supplementing pure H2(commonly referred to as chemical fertilizer hydrogen), the chemical fertilizer hydrogen can with after the gas mixing of above-mentioned return
Into in pre-hydrotreating reaction and/or the hydrogenation reaction, pre-hydrotreating reaction and/or the hydrogenation reaction can also be individually entered
In.
In the present invention, by the hydrogenation reaction products therefrom carry out gas-liquid separation obtained by liquid material can pass through or
Person is without subsequent treatment afterwards as the raw material in product or other techniques.For example, by the hydrogenation reaction products therefrom into
The liquid that the separating obtained liquid material of promoting the circulation of qi liquid obtains after desulfurization process is naphtha product, and naphtha product can be with
As ethylene cracking material, and in the process the method in tower top partial reflux can also be used to obtain pumice product.
In the present invention, by the method for hydrogenation reaction products therefrom progress gas-liquid separation, there is no particular limitation, example
Multi-stage separation can such as be passed through.A kind of specific embodiment according to the present invention, the hydrogenation reaction products therefrom is first in height
(temperature is 150-175 DEG C, pressure 3.2-3.8MPa) carries out first order separation under conditions of warm high pressure, and the first order is separated institute
Lightweight (temperature is 35-40 DEG C, pressure 3.3-3.5MPa) point under conditions of cryogenic high pressure carries out second level separation, by the
Separating obtained heavy part of level-one (temperature be 150-175 DEG C, pressure 0.9-1.1MPa) under conditions of high-temperature low-pressure carries out the
Three-level separates, and the third level separating obtained lightweight point is mixed with the separating obtained liquid in the second level or (is preferably mixed) in low temperature respectively
(temperature is 35-45 DEG C, pressure 0.9-1.1MPa) carries out fourth stage separation, the separating obtained gas of the fourth stage under conditions of low pressure
Follow-up process (being not dealt with the present invention) is collected or is directly entered, the separating obtained liquid of the fourth stage is separated with the third level
Gained heavy part, which mixes or (preferably mixes) respectively, is collected or carries out depriving hydrogen sulphide stripping processing, is stripped in the depriving hydrogen sulphide
Hydrogen sulfide, part lighter hydrocarbons and water during processing in material are removed, so as to obtain naphtha product and pumice product.Separately
Outside, the separating obtained gas in the second level is the gas for being used to be recycled back in the pre-hydrotreating reaction and/or the hydrogenation reaction,
In gas for can simply be handled before looping back, for example, desulfurization can be passed through, except alkane and pressurization after
It is recirculated back in pre-hydrotreating reaction and/or the hydrogenation reaction.
In the present invention, in order to more fully utilize the material and the energy in system, it is preferable that it is anti-that material reaches pre- hydrogenation
Should and/or hydrogenation reaction in the method for temperature include:The material of temperature higher in the material and system is subjected to heat exchange, example
Such as, heat exchange can be carried out with flowing out the material of pre-hydrogenator into the material of pre-hydrogenator, into hydrogenation reaction
The material of device can carry out heat exchange with flowing out the material of hydrogenation reactor, it is possible thereby to the energy of internal system is made full use of,
The effectively save energy;In the case where the heat that exchange obtains is inadequate, in addition can once be heated again.
Second aspect of the present invention provides a kind of light dydrocarbon and raffinates oil and the system of coker gasoline mixed hydrogenation, as shown in Figure 1,
Wherein, which includes light dydrocarbon raffinate oil sources, coker gasoline source, pre-hydrogenator R200 and hydrogenation reactor, the pre- hydrogenation
The entrance of reactor R200 is connected with light dydrocarbon raffinate oil sources, the outlet of pre-hydrogenator R200 and the entrance of hydrogenation reactor
Connection, the entrance of the hydrogenation reactor are also connected with coker gasoline source.
In the present invention, in order to make material just can reach before pre-hydrogenator R200 is entered temperature substantially and
Pressure, it is preferable that be additionally provided with and add on the connecting pipeline between the light dydrocarbon raffinate oil sources and the pre-hydrogenator R200
Press equipment and heating equipment.Wherein, the pressurized equipment can be feed pump, such as the pre- hydrogenation feed pump P205 shown in Fig. 1;
The heating equipment can be the various conventional equipment being used for material heating in this area, but in order to more fully utilize system
Material and the energy in system, it is preferable that the heating equipment includes pre- hydrogenation heat exchanger E271 and pre- hydrogenation heater E270, its
Described in the outlet of pre-hydrogenator R200 also connected with the pre- hydrogenation heat exchanger E271 so that light dydrocarbon is raffinated oil raw material with
The material of the outlet of pre-hydrogenator carries out heat exchange in the pre- hydrogenation heat exchanger E271, since light dydrocarbon is raffinated oil pre-
The temperature reached in hydrogenation heat exchanger E271 by heat exchange is not high enough, therefore can set pre- hydrogenation heater E270 again,
Continue to be heated to predetermined temperature for light dydrocarbon to be raffinated oil.
In the present invention, the system also includes additional diluent source, the additional diluent source and the pre-hydrotreating reaction
Device connects, and common progress pre-hydrotreating reaction is diluted for raffinating oil to light dydrocarbon.The transport pipeline of additional diluent can be
Optional position is incorporated to the transport pipeline that light dydrocarbon is raffinated oil, and is preferably incorporated to what light dydrocarbon was raffinated oil before pressurized equipment and hydrogenation plant
Transport pipeline;For example, the pipeline of additional diluent source connection is connected with the pipeline of pre- hydrogenation feed pump P205 entrances.The dilution
Agent source can also be connected with the pipeline of coker gasoline, for the pre-hydrotreating raffinated oil when light dydrocarbon when something goes wrong to coking
Gasoline provides diluent temporarily, or a part of diluent is supplemented when the diluent obtained by pre- hydrogenation system is not enough measured.This is carried
It can also include other conventional ancillary equipments such as diluent storage tank V206 and diluent pump P204 for the circuit of diluent.
In the present invention, the hydrogenation reactor can be the one or more of serial or parallel connection, R201 as shown in Figure 1
And R202.In order to make material just can reach temperature and pressure substantially before hydrogenation reactor is entered, it is preferable that Jiao
Change and be additionally provided with heat exchange unit on the connecting pipeline between gasoline source and the hydrogenation reactor, the heat exchange unit include one or
Multiple hydrogenation heat exchangers, E201, E202AB and E202CD as shown in Figure 1, the entrance and exit of the hydrogenation reactor with
The heat exchange unit connection, the material of material and the outflow hydrogenation reactor hence into the hydrogenation reactor is described
Exchange heat in heat exchange unit.As shown in Figure 1, into hydrogenation reactor material followed by hydrogenation heat exchanger E202CD,
E202AB and E201, flows out the material of hydrogenation reactor followed by hydrogenation heat exchanger E201, E202AB and E202CD, so that into
The material for entering the hydrogenation reactor and the material that flows out the hydrogenation reactor in hydrogenation heat exchanger E201, E202AB and
Exchange heat in E202CD, gradually risen hence into the temperature of the material of the hydrogenation reactor and flow out the hydrogenation reaction
The temperature of the material of device gradually reduces.The temperature and the temperature of material that the number of hydrogenation heat exchanger can reach as needed are come true
Fixed, number causes material to reach required temperature enough.
In the present invention, it is preferred to the outlet of the pre-hydrogenator R200 is sequentially communicated the heat exchange unit and institute
State hydrogenation reactor, that is to say, that the material of outflow pre-hydrogenator R200 enters the heat exchange unit, in the heat exchange unit
In mixed with coker gasoline so as to play the role of diluent, the mixture of gained enters in hydrogenation reactor jointly.Due to stream
The material for going out pre-hydrogenator R200 has certain temperature, therefore can be added to positioned at multiple hydrogenation heat exchangers
In some middle hydrogenation heat exchanger, by taking Fig. 1 as an example, the material of outflow pre-hydrogenator R200 can enter middle second
Hydrogenation heat exchanger E202AB, mixes in the second hydrogenation heat exchanger E202AB with coker gasoline.
In the present invention, gas-liquid separation can be carried out to the material that the hydrogenation reactor flows out, by isolated gas
Body circulation is returned in pre-hydrogenator R200 and/or hydrogenation reactor R201 and R201, isolated liquid is not handled or
Product is used as after simple process.The equipment that the gas-liquid separation process can use this area routine, it is a kind of excellent according to the present invention
The embodiment of choosing, the outlet of the hydrogenation reactor are connected with the entrance of high pressure hot separator V243, the high pressure hot separator
The lightweight sub-export of V243 is connected with the entrance of cold high pressure separator V202, the heavy sub-export of the high pressure hot separator V243
It is connected with the entrance of thermal low-pressure separators V244, heavy part outlet of the cold high pressure separator V202 is separated with the heat low
Entrance of the lightweight sub-export of device V244 with cold low separator V203 is connected, and heavy part of cold low separator V203 goes out
Mouth is connected with the entrance that heavy part of the thermal low-pressure separators V244 is exported with depriving hydrogen sulphide stripper T201, thus, point
Liquid from gained obtains product collection after depriving hydrogen sulphide stripper T201;In addition, the cold high pressure separator V202
Lightweight sub-export is connected with the entrance of the pre-hydrogenator R200 and/or the entrance of the hydrogenation reactor, is achieved in
Isolated gas circulation is returned in pre-hydrogenator R200 and/or hydrogenation reactor R201 and R201.Preferably, separate
To gas first carry out certain place before pre-hydrogenator R200 and/or hydrogenation reactor R201 and R201 is recycled back to
Reason, such as pressurization, desulfurization, except alkane, a kind of preferred embodiment according to the present invention, the cold high pressure separator V202's is light
The entrance of matter sub-export and the pre-hydrogenator R200 and/or between the entrance of the hydrogenation reactor according further to material
Flow to direction and be disposed with desulphurization of recycle hydrogen tower T203, recycle hydrogen liquid separation tank V204 and circulating hydrogen compressor C202.
Further, since pre-hydrotreating reaction and hydrogenation reaction need to consume H2, therefore, further need exist for supplementing pure H2(commonly referred to as
For chemical fertilizer hydrogen), which can be with entering pre-hydrotreating reaction and/or the hydrogenation reaction after the gas mixing of above-mentioned return
In, it can also individually enter in pre-hydrotreating reaction and/or the hydrogenation reaction.A kind of preferred embodiment according to the present invention,
The lightweight sub-export of the cold high pressure separator V202 is hydrogenated with instead with the entrance of the pre-hydrogenator R200 and/or with described
The access port that pure hydrogen pipeline is additionally provided between the entrance of device is answered, so that obtained by pure hydrogen and the cold high pressure separator V202
Enter after lightweight point mixing the pre-hydrogenator R200 and/or with the hydrogenation reactor.
In the present invention, separating obtained gas and/or chemical fertilizer hydrogen are recycled back to pre-hydrogenator and/or hydrogenation reactor
In pipeline access way there is no particular limitation, such as can be from multiple portions of pre-hydrogenator and/or hydrogenation reactor
Position introduces at the same time, can also in addition be introduced into the pipeline of liquid material input pre-hydrogenator and/or hydrogenation reactor.
In the present invention, the light dydrocarbon is raffinated oil and the system of coker gasoline mixed hydrogenation can also include other this areas
Conventional use of optional equipment, for example, can be set after light dydrocarbon raffinate oil sources and/or coker gasoline source raw material dehydration device from
And by the moisture removal in material, such as the FI401 in Fig. 1;Such as can the heat exchange unit and the hydrogenation reactor it
Between reaction heating furnace is set, such as the F201 in Fig. 1, which uses when system brings into operation and terminates operation, system
The heating furnace does not start in the process of running, and material is simply flowed through from heating furnace.
A kind of preferred embodiment according to the present invention, as shown in Figure 1, the light dydrocarbon of the present invention is raffinated oil and coker gasoline mixes
Close the system of hydrogenation and carry out light dydrocarbon using the system and raffinate oil and the method for coker gasoline mixed hydrogenation includes:
As shown in Figure 1, the light dydrocarbon from light dydrocarbon raffinate oil sources is raffinated oil along material pipeline first in raw material dehydration device FI401
Dehydration, then mix with the additional diluent from diluent storage tank V206 (mixed weight ratio be 1:3-15), gained after mixing
Material continues on material pipeline and is pressurized to 5-6MPa, in pre- hydrogenation heat exchanger E271 and pre- in hydrogenation feed pump P205 in advance successively
100-150 DEG C is heated in hydrogenation heater E270, makes carbon subsequently into pre-hydrotreating reaction is carried out in pre-hydrogenator R200
Five raffinate oil in diene hydrogenation saturation (reaction condition includes:Hydrogen-oil ratio is 200-500v/v, air speed 1.2-3.95h-1,
Pressure is 3.5-5.0MPa, and temperature is 100-150 DEG C), resulting material first flows through pre- hydrogenation along pipeline and changes after pre-hydrotreating reaction
Hot device E271 is heated so as to be raffinated oil using the heat of the material to the light dydrocarbon for entering pre-hydrogenator, then flows into heat exchange
In the second hydrogenation heat exchanger E202AB in unit, in second hydrogenation heat exchanger E202AB and from coker gasoline source and
It is (mixed through the coker gasoline mixing by feedstock oil surge tank V201, hydrogenating materials pump P201 and the 3rd hydrogenation heat exchanger E202CD
Composition and division in a proportion is 1:1-2.5), mixed material flows through reaction heating furnace F201 by the first hydrogenation heat exchanger E201 and adds into first
Hydrogen reactor R201 and the second hydrogenation reactor R202 carries out hydrogenation reaction, and (reaction condition includes:Hydrogen-oil ratio is 250-600v/v,
Air speed is 0.8-2h-1, pressure 3.5-4.5MPa, temperature is 210-275 DEG C), the material of gained is followed by first after reaction
Hydrogenation heat exchanger E201, the second hydrogenation heat exchanger E202AB and the 3rd hydrogenation heat exchanger E202CD are so as to into hydrogenation reactor
Material heated, subsequently into high pressure hot separator V243 under conditions of high temperature and pressure (temperature be 150-175 DEG C,
Pressure is 3.2-3.8MPa) first order separation is carried out, the separating obtained lightweight of the first order is separated in cold high pressure separator V202
(temperature is 35-40 DEG C, pressure 3.3-3.5MPa) carries out second level separation under conditions of cryogenic high pressure, and the first order is separated
Gained heavy part be introduced into thermal low-pressure separators V244 under conditions of high-temperature low-pressure (temperature be 150-175 DEG C, pressure 0.9-
The third level separation 1.1MPa) is carried out, the third level separating obtained lightweight point and the separating obtained liquid in the second level are introduced into cold low point
From (temperature is 35-45 DEG C, pressure 0.9-1.1MPa) carries out fourth stage separation under conditions of low-temp low-pressure in device V203, the
The separating obtained liquid of level Four, which is mixed with the separating obtained heavy part of the third level or (preferably mixed) respectively, introduces depriving hydrogen sulphide stripper
T201 carries out depriving hydrogen sulphide stripping processing, obtains refined naphtha product and pumice product;In addition, the gas that the second level is separating obtained
Body carries out desulfurization in desulphurization of recycle hydrogen tower T203, carries out in recycle hydrogen liquid separation tank V204 remove alkane successively, then by circulating
Hydrogen compressor C202 is forced into after 4-7MPa and mixes Posterior circle with from the chemical fertilizer hydrogen (pure hydrogen) that exterior pressure is 4-7MPa
Into hydrogenation reactor R201 and R202, in pre-hydrogenator R200, and it is recycled to the pipeline of pre-hydrogenator R200
In.Thus, system of the invention and mode can realize the hydrotreating that light dydrocarbon is raffinated oil with coker gasoline, solve existing skill
The problem of art easy coking, resource can be reasonably utilized, is effectively reduced cost of material and energy loss, and can be effective
Extend the cycle of operation of equipment.
The present invention will be described in detail by way of examples below.
Embodiment 1-6 and comparative example 1-2 is used to illustrating that the light dydrocarbon of the present invention to be raffinated oil and coker gasoline mixed hydrogenation is
System and carry out light dydrocarbon using the system and raffinate oil and the method for coker gasoline mixed hydrogenation.
In following comparative example and embodiment, the component and content that light dydrocarbon used is raffinated oil are as shown in table 1, coker gasoline
Component and content it is as shown in table 2.
Table 1
Table 2
Table 3
Density (20 DEG C)/g.cm-3 | 0.67 |
Boiling range/DEG C | |
IBP | 69 |
10% | 76 |
50% | 84 |
90% | 103 |
EBP | 137 |
Bromine valency/gBr (100g)-1 | 24 |
Sulphur/μ g.g-1 | 0.5 |
Nitrogen/μ gg | <0.5 |
Embodiment 1
As shown in Figure 1, the light dydrocarbon from light dydrocarbon raffinate oil sources is raffinated oil, (1 parts by weight) first take off along material pipeline in raw material
Hydrophone FI401 is dehydrated, and then (7 parts by weight, fill by upstream Aromatics Extractive Project with the additional diluent from diluent storage tank V206
Put the mode directly fed to obtain, component is as shown in table 3, and additional diluent used below is identical with the present embodiment) mixing,
Resulting material continues on material pipeline and is being pressurized to 6.0MPa successively in hydrogenation feed pump P205 in advance, is being changed in pre- hydrogenation after mixing
120 DEG C are heated in hot device E271 and pre- hydrogenation heater E270, subsequently into being hydrogenated with advance in pre-hydrogenator R200
Reaction make light dydrocarbon raffinate oil in diene hydrogenation saturation (reaction condition includes:Hydrogen-oil ratio is 250v/v, air speed 3.0h-1, pressure
Power is 4.5MPa, and temperature is 145 DEG C;Using the catalyst without heavy metal, producer is sinopec Fushun catalyst branch company, board
Number it is FHUDS-6/FH-40C), resulting material first flows through pre- hydrogenation heat exchanger E271 along pipeline so as to profit after pre-hydrotreating reaction
Raffinated oil and heated to the light dydrocarbon for entering pre-hydrogenator with the heat of the material, second then flowed into heat exchange unit adds
In hydrogen heat exchanger E202AB, delay in second hydrogenation heat exchanger E202AB with coming from coker gasoline source and having already passed through feedstock oil
Coker gasoline (12 parts by weight) mixing of tank V201, hydrogenating materials pump P201 and the 3rd hydrogenation heat exchanger E202CD are rushed, after mixing
Material flow through reaction heating furnace F201 by the first hydrogenation heat exchanger E201 and added into hydrogenation reactor R201 and R202
(reaction condition includes for hydrogen reaction:Hydrogen-oil ratio is 400v/v, air speed 1.6h-1, pressure 4.5MPa, temperature is 230 DEG C), reaction
The material of gained is followed by the first hydrogenation heat exchanger E201, the second hydrogenation heat exchanger E202AB and the 3rd hydrogenation heat exchanger afterwards
E202CD so as to enter hydrogenation reactor material heat, subsequently into high pressure hot separator V243 in high temperature and pressure
Under conditions of (temperature be 160 DEG C, pressure 3.6MPa) carry out first order separation, the separating obtained lightweight of the first order is separated into cold
(temperature is 40 DEG C, pressure 3.4MPa) carries out second level separation under conditions of cryogenic high pressure in high-pressure separator V202, will
The separating obtained heavy part of the first order be introduced into thermal low-pressure separators V244 under conditions of high-temperature low-pressure (temperature be 160 DEG C, pressure
For 1.1MPa) third level separation is carried out, the third level separating obtained lightweight point and the separating obtained liquid in the second level are introduced into cold low
(temperature is 40 DEG C, pressure 1.1MPa) carries out fourth stage separation, the fourth stage under conditions of low-temp low-pressure in separator V203
Separating obtained liquid, which is mixed with the separating obtained heavy part of the third level or (preferably mixed) respectively, introduces depriving hydrogen sulphide stripper T201
Depriving hydrogen sulphide stripping processing is carried out, obtains refined naphtha product (being denoted as I1) and pumice product;In addition, the second level is separating obtained
Gas desulfurization is carried out in desulphurization of recycle hydrogen tower T203 successively, carries out in recycle hydrogen liquid separation tank V204 removing alkane, then pass through
Circulating hydrogen compressor C202 be forced into after 5.0MPa with mixed from the chemical fertilizer hydrogen (pure hydrogen) that exterior pressure is 7.0MPa after
It is recycled in hydrogenation reactor R201 and R202, in pre-hydrogenator R200, and is recycled to pre-hydrogenator R200's
In pipeline.Thus, system of the invention and mode can realize the hydrotreating that light dydrocarbon is raffinated oil with coker gasoline, solve existing
There is the problem of technology easy coking, can reasonably utilize resource, be effectively reduced cost of material and energy loss, and can
Effectively extend the cycle of operation of equipment.
Embodiment 2
Carried out according to the system and method for embodiment 1, the difference is that the pre-hydrotreating reaction in pre-hydrogenator R200
Condition includes:Hydrogen-oil ratio is 200v/v, air speed 1.6h-1, pressure 3.8MPa, temperature is 100 DEG C;The light dydrocarbon raffinates oil,
The weight ratio of the dosage of additional diluent and coker gasoline is 1:6:12.The naphtha product of gained is denoted as I2.
Embodiment 3
Carried out according to the system and method for embodiment 1, the difference is that the pre-hydrotreating reaction in pre-hydrogenator R200
Condition includes:Hydrogen-oil ratio is 350v/v, air speed 3.95h-1, pressure 5.0MPa, temperature is 130 DEG C;The light dydrocarbon raffinates oil,
The weight ratio of the dosage of additional diluent and coker gasoline is 1:8:16.The naphtha product of gained is denoted as I3.
Embodiment 4
Carried out according to the system and method for embodiment 1, the difference is that the pre-hydrotreating reaction in pre-hydrogenator R200
Condition includes:Hydrogen-oil ratio is 400v/v, air speed 1.5h-1, pressure 3.7MPa, temperature is 135 DEG C.The naphtha of gained is produced
Product are denoted as I4.
Embodiment 5
Carried out according to the system and method for embodiment 1, the difference is that the light dydrocarbon is raffinated oil, additional diluent and Jiao
The weight ratio for changing the dosage of gasoline is 1:7:20.The naphtha product of gained is denoted as I5.
Embodiment 6
Carried out according to the system and method for embodiment 1, the difference is that catalyst used in pre-hydrotreating reaction be containing
The heavy metal catalyst of the Pd of 0.258 weight %, producer are sinopec Fushun catalyst branch company, trade mark SHP-01.By institute
The naphtha product obtained is denoted as I6.
Comparative example 1
Carry out according to the system and method for embodiment 1, the difference is that the step of without pre-hydrotreating reaction, do not introduce
Light dydrocarbon is raffinated oil, and directly will carry out hydrogenation reaction with the additional diluent of the coker gasoline of 12 parts by weight and 8 parts by weight, that is,
Say, remove and light dydrocarbon raffinate oil sources, raw material dehydration tower FI401, pre- hydrogenation feed pump P205, pre- hydrogenation heat exchanger are provided with Fig. 1
The route of E271, pre- hydrogenation heater E270 and pre-hydrogenator R200.The naphtha product of gained is denoted as D1.
Comparative example 2
Carried out according to the system and method for comparative example 1, the difference is that not introducing coker gasoline, will directly use 2.5 weight
The light dydrocarbon of part is raffinated oil and the additional diluent of 17.5 parts by weight carries out hydrogenation reaction.The naphtha product of gained is denoted as D2.
Test case
Embodiment 1-6 and comparative example 1-2 are tested as follows respectively, by acquired results note in table 4.
(1) pre-hydrogenator for measuring embodiment 1-6 respectively according to method as defined in GZHLH-T4.102.23.336 goes out
The diene content (m/m) of mouth resulting material, since comparative example 1 and 2 is without the process of pre-hydrotreating reaction, without the inspection
Survey;
(2) sulfur content of gained naphtha product I1~I6 and D1~D2 is measured respectively according to method as defined in SH-T0253
(mg/kg);
(3) bromine valency of gained naphtha product I1~I6 and D1~D2 is measured respectively according to method as defined in SH-T0236
(gBr/100g);
(4) the entrance pressure difference indicator of E201, E202AB, E202CD of embodiment 1-6 and comparative example 1-2 are read respectively
The data (i.e. the pressure difference in exit and inlet) of table, are their own shell side pressure difference.
Table 4
As can be seen from Table 4, the diene content of the obtained pre-hydrotreating reaction resulting material of the method according to the invention
It can reach below 1 weight %, can be obtained with reference to the preprocessing process that other detection parameters can be seen that by the present invention
More preferable naphtha product simultaneously reduces coking.The sulfur content of naphtha product obtained by the method according to the invention and system can be with
Reach below 20mg/kg or even below 15mg/kg can be reached, bromine valency, which can reach, is even up to 0.06 below 0.08 weight %
Below weight %, it was demonstrated that the naphtha product of present invention gained has very high purity;The E201 shell sides pressure difference of the present invention can be with
Reach below 7kPa and be even up to below 4kPa, E202AB shell sides pressure difference of the invention can reach below 30kPa even up to
Below 25kPa, E202CD shell sides pressure difference of the invention can reach below 40kPa and be even up to below 35kPa, it can be seen that
The shell side pressure difference of the present invention is smaller, it was demonstrated that coking amount is less in system of the invention, therefore the system of the present invention can be realized more
The long cycle of operation (cycle of operation of the invention can reach more than 1500 days).And in the naphtha product of the gained of comparative example 1
Sulfur content reaches 50mg/kg, and bromine valency reaches 2.0 weight %, and shell side pressure difference is also significantly larger than of the invention, it was demonstrated that coking situation
The present invention is much worse than, therefore the cycle of operation is also (being typically only 700 days or so) significantly shorter than of the invention.And comparative example 2 makes
In the case of substantial amounts of diluent, the content of its bromine valency is still up to 1.0 weight %, shell side pressure difference remain on it is very high, therefore
(temperature, pressure) needs more diluents so as to which cost is higher to this method under the same conditions, and is hydrogenated with effect and control
The effect of coking processed is also not ideal enough.
In addition, by being adjusted according to the energy saving inspection center of Ningbo Institute of Technology, Zhejiang University, the embodiment of the present invention 1 and contrast
Example 1 is compared, and amount of energy saving has reached 130.97 tons of standard coals, it can be seen that the present invention can reasonably utilize resource, effectively drop
Low cost of material and energy loss.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrate various combinations of possible ways.In addition, a variety of implementations of the present invention
It can also be combined between mode, as long as it without prejudice to the thought of the present invention, it is public that it should equally be considered as institute of the invention
The content opened.
Claims (12)
1. a kind of light dydrocarbon is raffinated oil and the method for coker gasoline mixed hydrogenation, it is characterised in that this method includes:By light dydrocarbon raffinate
Oil carry out pre-hydrotreating reaction so that the light dydrocarbon raffinate oil in diene hydrogenation saturation, by the pre-hydrotreating reaction products therefrom
Hydrogenation reaction is carried out jointly as diluent and coker gasoline.
2. according to the method described in claim 1, wherein, the pre-hydrotreating reaction cause the light dydrocarbon raffinate oil in alkadienes
Hydrogenation saturation and the light dydrocarbon of more than 90 weight %, which are raffinated oil, does not occur monoolefin hydrogenation reaction, desulphurization reaction or denitrification reaction;
Preferably, the temperature of the pre-hydrotreating reaction is 100-150 DEG C, and catalyst is the hydrogenation catalyst for not containing heavy metal;
Preferably, the condition of the pre-hydrotreating reaction includes:Hydrogen-oil ratio is 200-500v/v, air speed 1.2-3.95h-1, pressure
For 3.5-5MPa.
3. method according to claim 1 or 2, wherein, the method further includes:Introduce additional diluent and the light dydrocarbon
Raffinate oil and carry out pre-hydrotreating reaction jointly, it is 1 that the light dydrocarbon, which is raffinated oil with the weight ratio of the dosage of the additional diluent,:3-
15。
4. method according to claim 1 or 2, wherein, the mixing of the pre-hydrotreating reaction products therefrom and coker gasoline
Than for 1:1-2.5 it is preferably 1:1.5-2.
5. according to the method described in claim 1, wherein, the condition of the hydrogenation reaction includes:Hydrogen-oil ratio is 250-600v/v,
Air speed is 0.8-2h-1, pressure 3.5-4.5MPa, temperature is 210-275 DEG C.
6. method according to claim 1 or 2, wherein, the method further includes:By the hydrogenation reaction products therefrom into
Row gas-liquid separation, gained gas circulation is returned in the pre-hydrotreating reaction and/or the hydrogenation reaction.
7. a kind of light dydrocarbon is raffinated oil and the system of coker gasoline mixed hydrogenation, it is characterised in that the system is raffinated oil including light dydrocarbon
Source, coker gasoline source, pre-hydrogenator (R200) and hydrogenation reactor, the entrance and light dydrocarbon of the pre-hydrogenator (R200)
Raffinate oil sources connects, and the outlet of the pre-hydrogenator (R200) is connected with the entrance of hydrogenation reactor, the hydrogenation reactor
Entrance also connected with coker gasoline source.
8. system according to claim 7, wherein, the light dydrocarbon raffinate oil sources and the pre-hydrogenator (R200) it
Between connecting pipeline on be additionally provided with pressurized equipment and heating equipment;
Preferably, the heating equipment includes pre- hydrogenation heat exchanger (E271) and pre- hydrogenation heater (E270), wherein described pre-
The outlet of hydrogenation reactor (R200) is also connected with the pre- hydrogenation heat exchanger (E271), raw material and pre-add so that light dydrocarbon is raffinated oil
The material of the outlet of hydrogen reactor carries out heat exchange in the pre- hydrogenation heat exchanger (E271).
9. system according to claim 7, wherein, the communicating pipe between the coker gasoline source and the hydrogenation reactor
Heat exchange unit is additionally provided with road, which includes one or more hydrogenation heat exchangers, the entrance of the hydrogenation reactor
Connected with outlet with the heat exchange unit, the material and the outflow hydrogenation reactor hence into the hydrogenation reactor
Material exchanges heat in the heat exchange unit;
Preferably, the outlet of the pre-hydrogenator (R200) is sequentially communicated the heat exchange unit and the hydrogenation reactor.
10. according to the system described in any one in claim 7-9, wherein, the outlet of the hydrogenation reactor and thermal high
The entrance of separator (V243) is connected, lightweight sub-export and the cold high pressure separator (V202) of the high pressure hot separator (V243)
Entrance is connected, and the heavy sub-export of the high pressure hot separator (V243) is connected with the entrance of thermal low-pressure separators (V244), institute
State heavy part outlet of cold high pressure separator (V202) and the lightweight sub-exports of the thermal low-pressure separators (V244) with it is cold low
The entrance of pressure separator (V203) is connected, the outlet of heavy part and the thermal low-pressure separators of the cold low separator (V203)
(V244) entrance that heavy part exports with depriving hydrogen sulphide stripper (T201) is connected.
11. system according to claim 10, wherein, the lightweight sub-export of the cold high pressure separator (V202) with it is described
The entrance connection of the entrance and/or the hydrogenation reactor of pre-hydrogenator (R200);
Preferably, the lightweight sub-export of the cold high pressure separator (V202) and the entrance of the pre-hydrogenator (R200)
And/or desulphurization of recycle hydrogen tower is disposed with according further to flow direction of material direction between the entrance of the hydrogenation reactor
(T203), recycle hydrogen liquid separation tank (V204) and circulating hydrogen compressor (C202);
Preferably, the lightweight sub-export of the cold high pressure separator (V202) and the entrance of the pre-hydrogenator (R200)
And/or the access port of pure hydrogen pipeline is additionally provided between the entrance of the hydrogenation reactor, so that pure hydrogen and described cold
Enter after lightweight obtained by high-pressure separator (V202) point mixing the pre-hydrogenator (R200) and/or with the hydrogenation reaction
Device.
12. system according to claim 7, wherein, the system also includes additional diluent source, the additional diluent source
The pipeline of connection is connected with the pipeline of pre- hydrogenation feed pump (P205) entrance.
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CN102234537A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Hydrogenation method for ethylene tar |
CN102827632A (en) * | 2011-06-14 | 2012-12-19 | 中国石油化工股份有限公司 | Method for processing C5 raffinate from ethene cracking |
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CN102234537A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Hydrogenation method for ethylene tar |
CN102827632A (en) * | 2011-06-14 | 2012-12-19 | 中国石油化工股份有限公司 | Method for processing C5 raffinate from ethene cracking |
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