CN106609160B - A method of separation coking dry gas - Google Patents
A method of separation coking dry gas Download PDFInfo
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- CN106609160B CN106609160B CN201510702299.XA CN201510702299A CN106609160B CN 106609160 B CN106609160 B CN 106609160B CN 201510702299 A CN201510702299 A CN 201510702299A CN 106609160 B CN106609160 B CN 106609160B
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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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/02—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by hydrogenation
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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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/043—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by fractional condensation
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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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to dry gas process fields, disclose a kind of method of separation coking dry gas, and this method includes：Coking dry gas is carried out to catalytic hydrogenation treatment, cooling treatment and four absorbent absorption of carbon processing successively, then gaseous phase materials and liquid phase material that four absorbent absorption of carbon is handled are subjected to gasoline absorbent respectively and absorb processing and four desorption of carbon processing, the gaseous phase materials that recycling four desorption of carbon is handled, and the liquid phase material that four desorption of carbon is handled is back to four absorbent absorption of carbon processing.The method of the present invention has the characteristics that investment is small, low energy consumption, four absorbent internal circulating load of carbon is small.
Description
Technical field
The present invention relates to dry gas process fields, and in particular, to a method of separation coking dry gas.
Background technology
Refinery's coking dry gas derives from refinery's delayed coking unit, and the ethane molar content in usual coking dry gas accounts for about
20%, for ethylene molar content 2% or more, remaining group is divided into methane, hydrogen, propane, saturated water etc..Refinery's coking dry gas at present
It is burnt up mainly as fuel, utility value is relatively low.If the ethane component in coking dry gas recycled, ethylene plant is sent to as second
The raw material of alkane pyrolysis furnace can save cracking stock oil, reduce production cost of ethylene, and economic benefit and social benefit ten are clearly demarcated
It is aobvious.
Currently, the method for recycling two component of carbon from refinery's coking dry gas mainly has separation by deep refrigeration, pressure swing adsorption method, shallow
Cold oil absorption process etc., various methods differ from one another.Separation by deep refrigeration technical maturity, Recovery rate of ethylene is high, but invests greatly, for dilute
Ethylene recovery energy consumption is higher；Pressure swing adsorption method is easy to operate, and energy consumption is relatively low, but product purity is low, and Recovery rate of ethylene is low, takes up an area face
Product is big.
Shallow cold oil absorption process mainly detaches gas mixing using absorbent to the different solubility of each component in gas
Object generally absorbs the heavy constituent of C2 and C2 or more first with absorbent, isolates the fixed gases such as methane, hydrogen, then use rectification method
Each component in separate absorbent agent.This method has the C2C3 rate of recovery high, and production safety is reliable for operation, the adaptation to unstripped gas
Property it is strong the features such as, be one of current competitive technology.But for coking dry gas recycle, due in coking dry gas containing compared with
More hydrogen and ethylene can be such that the partial pressure of ethane reduces, in order to ensure assimilation effect during C-4-fraction absorbs ethane
And ethane recovery, four absorbent of larger amount of carbon need to be used, therefore recycled between four absorption tower of carbon, four desorber of carbon
Four absorbent of carbon it is more, the load of four desorber tower reactor reboiler of four absorption tower tower reactor reboiler of carbon and carbon is higher, affects
The energy consumption of whole device.
The method that CN 101063048A disclose cold oil absorption process separating plant dry gas in a kind of use, the technique is by pressing
Contracting, removing sour gas, drying and purification, absorption, desorption, cold recovery and rough segmentation and etc. composition, there is absorbent cost
It is cheap, lose low advantage.But it needs dry gas being cooled to -30 DEG C to -40 DEG C in the technique, cold separating technology in belonging to, therefore
Invest larger, energy consumption is higher.
CN 103087772A disclose a kind of device and method of oil-absorption process separation dry gas, this method absorbs by carbon four,
The desorption of carbon four, gasoline absorb and etc. composition, absorbent is used as using carbon four, two C3 fraction of carbon in dry gas is recycled, then adopts
The carbon four in tail gas is recycled with gasoline absorbent.Two rate of recovery of technique carbon is high, and the loss of four absorbent of carbon is few, but four absorbent of carbon
Internal circulating load is larger, affects the energy consumption of device.
CN 104557387A disclose a kind of refinery's mixing dry gas recovery system, including absorption tower, desorber, purification dress
It sets, crude tower, naphtha scrubber and gasoline desorber.The technique recycles the carbon in dry gas by a set of four absorptions of carbon-desorption
Two components, then recycle by a set of gasoline absorption-desorption four absorbent of carbon of entrainment.The technique can recycle the suction of carbon four
Agent and gasoline absorbent are received, absorbent dosage is few, and loss is few.But the four absorbent dosage of carbon on absorption tower is larger, in absorption tower, solution
The amount for inhaling four absorbent of carbon recycled between tower, gasoline desorber is more, and plant energy consumption is higher.
In conclusion the method for existing separating plant coking dry gas, there is investments greatly, high energy consumption, four absorbent of carbon
The big problem of internal circulating load.
Invention content
The purpose of the invention is to overcome to invest big, energy consumption present in existing separating plant coking dry gas method
Problem high, four absorbent internal circulating load of carbon is big provides a kind of method of separation coking dry gas, and this method, which has, invests small, energy consumption
Low, the features such as four absorbent internal circulating load of carbon is small.
To achieve the goals above, the present invention provides a kind of method of separation coking dry gas, this method includes：By coking
Dry gas carries out catalytic hydrogenation treatment, cooling treatment and four absorbent absorption of carbon processing successively, then will be at four absorbent absorption of carbon
It manages obtained gaseous phase materials and liquid phase material carries out gasoline absorbent and absorbs processing and four desorption of carbon processing respectively, recycling carbon four solves
The gaseous phase materials that suction is handled, and the liquid phase material that four desorption of carbon is handled is back to four absorbent absorption of carbon processing.
The method of the separation coking dry gas of the present invention, has the following advantages：
(1) in method of the invention, coking dry gas first carries out catalytic hydrogenation treatment before entering shallow cold oil absorptive unit, subtracts
The content for having lacked hydrogen and ethylene in the charging of shallow cold oil absorptive unit enhances assimilation effect of four absorbent of carbon to ethane,
To reduce four absorbent internal circulating load of carbon, plant energy consumption is reduced.
(2) it in method of the invention, is evaporated for recycling C2C3 in coking dry gas (material that i.e. catalytic hydrogenation treatment obtains)
Four absorbent of carbon divided and the gasoline absorbent for recycling four absorbent of carbon carried secretly in four absorption tower tower top tail gas of carbon, it is former
Material is easy to get, of low cost.
(3) in method of the invention, the gaseous phase materials that four desorption of carbon is handled are rich ethane gas, and olefin(e) centent reaches
In Cracking Feedstock requirement need not be mixed into other saturation dry gas in coking dry gas charging.
(4) in method of the invention, the methane content in rich ethane gas will not increase downstream ethylene unit and split in 1-5%
Solve the specific energy consumption of stove and piece-rate system.
(5) in method of the invention, the C2C3 fractions in coking dry gas are absorbed with four absorbent of carbon, technological process is not required to second
Alkene, propylene refrigeration compressor and expanding machine, it is 5-15 DEG C to absorb temperature, and lithium bromide refrigerator can be selected and provide refrigerant to make
Cold, small investment, easy to operate, low energy consumption.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the structural schematic diagram that the device that coking dry gas uses is detached in the present invention.
Reference sign
1 residue gas compressor；2 hydrogenation reactors；3 dry gas coolers；4 carbon, four absorption tower；5 carbon, four desorber；6 carbon four cool down
Device；7 naphtha scrubbers.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method of separation coking dry gas, this method includes：Coking dry gas is catalyzed successively
Hydrotreating, cooling treatment and four absorbent absorption of carbon processing, the gaseous phase materials for then handling four absorbent absorption of carbon
It carries out gasoline absorbent respectively with liquid phase material and absorbs processing and four desorption of carbon processing, the gas phase that recycling four desorption of carbon is handled
Material, and the liquid phase material that four desorption of carbon is handled is back to four absorbent absorption of carbon processing.
In the method for the present invention, for the source of coking dry gas, there is no particular limitation, can be common each in this field
Kind source, such as refinery's delayed coking unit is can come from, the pressure of the coking dry gas from refinery's delayed coking unit is general
In 0.4-0.8MPaG, catalytic hydrogenation treatment is carried out for convenience, under preferable case, this method further includes in catalytic hydrogenation treatment
Before, coking dry gas is subjected to compression processing improving the pressure of coking dry gas to 3-5MPaG；It is further preferred that at compression
Reason is that multi-stage compression is handled.Wherein, the hop count of compression processing is not provided particularly, such as can is at three sections of compressions
Reason.
In the method for the present invention, for the method for catalytic hydrogenation treatment, there is no particular limitation, can be commonly used in the art
Various methods, under preferable case, the method for catalytic hydrogenation treatment includes：Coking dry gas is contacted with hydrogenation catalyst, temperature
It is 60-300 DEG C, further preferably 150-220 DEG C；Pressure is 1-5MPaG, further preferably 3-4MPaG；Volume space velocity is
50-1000h-1, further preferably 100-500h-1.It will be appreciated by persons skilled in the art that being contacted with hydrogenation catalyst
Coking dry gas be preferably material that compression processing obtains.
For hydrogenation catalyst, there is no particular limitation, can be various hydrogenation catalysts commonly used in the art, it is preferable that
Hydrogenation catalyst is the hydrogenation catalyst containing at least one of Co, Mo, Ni and W system metal metal, further preferably Co-
Mo-Ni series hydrocatalysts.
The catalytic hydrogenation treatment of the present invention is used for the olefins hydrogenation in coking dry gas at alkane, by above-mentioned catalysis
Olefin(e) centent is not more than 0.1 mole of % in the material that hydrotreating obtains.
In the case of process of the present invention it is preferred, the condition of cooling treatment includes：The material that catalytic hydrogenation treatment is obtained
It is cooled to 5-15 DEG C.It is further preferred that the cold water that the refrigerant that cooling treatment uses is prepared for lithium-bromide absorption-type refrigerating machine,
Temperature can be 5 DEG C or 7 DEG C.
In the case of process of the present invention it is preferred, after the liquid phase material that four desorption of carbon is handled is cooled to 5-15 DEG C
It is back to four absorbent absorption of carbon processing.
In the case of process of the present invention it is preferred, the method that four absorbent of carbon absorbs processing includes：Cooling treatment is obtained
Material supply to making it be contacted with four absorbent of carbon in four absorption tower of carbon, the number of theoretical plate on four absorption tower of carbon is 25-50, operation
Pressure is 3-4.6MPaG, and tower top temperature is 10-30 DEG C, and bottom temperature is 100-160 DEG C.
It will be understood by those skilled in the art that supplying the material that cooling treatment obtains to making it in four absorption tower of carbon
The embodiment contacted with four absorbent of carbon can be：Four absorbent of carbon is sprayed at the top of four absorption tower of carbon, is inhaled with from carbon four
The coking dry gas material counter current contacting entered in the middle part of tower is received, four absorbent of carbon absorbs C2 fractions and more heavy constituent in material, so
Afterwards by gaseous phase materials (the predominantly unabsorbed methane, hydrogen body) supply from four absorption tower tower top of carbon to naphtha scrubber
Four absorbent of carbon wherein carried secretly is recycled, supply is extremely by the liquid phase material (i.e. four absorbent of rich carbon) from four absorption tower tower reactor of carbon
The processing of four desorber of carbon.Due to there is four absorbent of a small amount of carbon that can send out battery limit (BL) with naphtha scrubber kettle liquid, in order to ensure system
The carbon four on four absorption tower of middle carbon absorbs agent flux, it is preferable that when carrying out the absorption processing of four absorbent of carbon, into four absorption tower of carbon
Supplement four absorbent of fresh carbon.The temperature of four absorbent of fresh carbon to supplement itself does not specially require, as long as supplying to carbon
Temperature when four absorption towers is 5-15 DEG C.For operating easily, preferably, by four absorbent of fresh carbon of supplement with come from
The liquid phase material mixing of four desorber tower reactor of carbon is latter and is cooled down, and four absorption tower of carbon is then sent to.
It will be understood by those skilled in the art that four absorbent of carbon in the present invention is to be carried out in four absorption tower of carbon
Various absorbents when four absorbent of carbon absorbs processing for absorbing C2 fractions and more heavy constituent in coking dry gas material.Specifically
Ground, for four absorbent of carbon, there is no particular limitation, can be various C-4-fractions commonly used in the art, under preferable case, carbon
Four absorbents be from refinery containing C-4-fraction material (including mixing C-4-fraction, after ether C-4-fraction or other with
Fraction based on carbon four), the further preferably normal butane from refinery.The dosage of four absorbent of carbon is not limited particularly
Fixed, those skilled in the art can determines according to actual conditions, this is known to those skilled in the art, and details are not described herein.
In the case of process of the present invention it is preferred, the method for the desorption processing of carbon four includes：Four absorbent absorption of carbon is handled
Obtained liquid phase material is supplied to four desorber of carbon, and the number of theoretical plate of four desorber of carbon is 20-50, operating pressure 1.5-
2.8MPaG, tower top temperature are 15-70 DEG C, and bottom temperature is 110-200 DEG C.
It will be understood by those skilled in the art that supplying the liquid phase material that four absorbent absorption of carbon is handled to carbon
Embodiment in four desorbers can be the liquid phase material from four absorption tower tower reactor of carbon (i.e. four absorbent of rich carbon) supply in the future
To in the middle part of four desorber of carbon, it is rich ethane gas product to desorb the gaseous phase materials that column overhead obtains in carbon four, in four desorber tower of carbon
The liquid phase material that kettle obtains is four absorbent of poor carbon, and four absorption tower of carbon is returned to after which is cooled to 5-15 DEG C and is followed
Ring uses.Mainly contained in aforementioned obtained rich ethane gas product the ethane of 60-95 moles of %, the ethylene of 0.01-2 moles of %,
The third heavy constituent of carbon of the methane of 0.5-5 moles of %, 3-40 moles of %, remaining ingredient are impurity, such as nitrogen, carbon monoxide,
Raw material as ethane cracking furnace is can be supplied to the pyrolysis furnace of ethylene unit.
In the case of process of the present invention it is preferred, the method that gasoline absorbent absorbs processing includes：Four absorbent of carbon is inhaled
The gaseous phase materials that receipts are handled are supplied to making it be contacted with gasoline absorbent in naphtha scrubber, the theoretical plate of naphtha scrubber
Number is 15-25, and operating pressure 2.7-4.5MPaG, tower top temperature is 10-40 DEG C, and bottom temperature is 20-60 DEG C.
It will be understood by those skilled in the art that supplying the gaseous phase materials that four absorbent absorption of carbon is handled to vapour
Its embodiment contacted with gasoline absorbent is set to be in oil-absorption tower：By the gaseous phase materials from four absorption tower tower top of carbon
(predominantly unabsorbed methane, hydrogen body) supply to naphtha scrubber bottom, gasoline absorbent enters from tower top, makes gas phase
Material is contacted with gasoline absorbent, and gasoline absorbent absorbs four absorbent of carbon carried secretly in gaseous phase materials, naphtha scrubber tower top
Gaseous phase materials and liquid phase material are respectively obtained with tower reactor, gaseous phase materials are sent out into battery limit (BL), by liquid phase material carrying device.It is preferred that
Ground, method of the invention further include：The gaseous phase materials that gasoline absorbent absorption is handled are supplied to fuel gas storage element,
The liquid phase material that gasoline absorbent absorption is handled is subjected to separating treatment to recycle four absorbent of carbon and gasoline.Gasoline is inhaled
It can be by vapour to receive the liquid phase material that agent absorption is handled and carry out separating treatment in the method for recycling four absorbent of carbon and gasoline
The liquid phase material of oil-absorption tower tower reactor is sent to oil plant absorption-four absorbent of stabilising arrangement separation of carbon and gasoline fraction, this is this
Well known to field technology personnel, details are not described herein.
It will be understood by those skilled in the art that the gasoline absorbent in the present invention is to be carried out in naphtha scrubber
For absorbing four absorbent of carbon etc. carried secretly in the gaseous phase materials from four absorption tower tower top of carbon when gasoline absorbent absorbs processing
The various absorbents of component.For gasoline absorbent, there is no particular limitation, can be that various gasoline commonly used in the art absorb
Agent, under preferable case, gasoline absorbent is one or more in gasoline, naphtha and heavy naphtha from refinery, wherein
Gasoline is more preferably the stable gasoline from refinery.For the dosage of gasoline absorbent, there is no particular limitation, this field
Technical staff can determines according to actual conditions, this is known to those skilled in the art, and details are not described herein.
Embodiment
Below with reference to Fig. 1 and by embodiment, the present invention will be described in detail, but is not intended to limit the present invention.
In following embodiment and comparative example, the composition of the coking dry gas from refinery's delayed coking unit is (burnt as shown in table 1
It is impurity, such as nitrogen, carbon monoxide to change remaining ingredient in dry gas, is not shown).
Table 1
| Coking dry gas | |
| Temperature, DEG C | 40 |
| Pressure, MPaG | 0.6 |
| Mass flow, t/h | 10.0 |
| Composition, mol% | |
| H2O | 0.73 |
| H2 | 11.73 |
| CH4 | 59.81 |
| C2H6 | 21.85 |
| C2H4 | 2.81 |
| C3H6 | 3.05 |
Embodiment 1
The method that the present embodiment is used to illustrate the separation coking dry gas of the present invention.
The coking dry gas that pressure from refinery's delayed coking unit is 0.6MPaG is supplied to residue gas compressor 1, is passed through
Three sections of compression processings improve dry gas pressure to 4MPaG.Then dry gas after supercharged is supplied to hydrogenation reactor 2, and adds hydrogen
Catalyst Co-Mo-Ni series catalysts (are purchased from Sinopec Beijing Research Institute of Chemical Industry, model BY-5)
Catalytic hydrogenation reaction occurs for contact, and controlling reaction temperature is 180 DEG C, reaction pressure 4MPaG, volume space velocity 100h-1, add hydrogen
Ethylene molar content is down to 0.1% in 2 exit gas of reactor.Then the exit gas of hydrogenation reactor 2 is cooled down through dry gas
Device 3 is cooled to 15 DEG C with 7 DEG C of cold water prepared by lithium-bromide absorption-type refrigerating machine, and supplies to the middle part on four absorption tower 4 of carbon.
In four absorption tower 4 of carbon, uses refinery's normal butane as four absorbent (flow 21.4t/h) of carbon, inhaled from carbon four
The tower top for receiving tower 4 sprays into and dry gas counter current contacting.Wherein, the number of theoretical plate on four absorption tower 4 of carbon is 40, and operating pressure is
3.8MPaG, tower top temperature are 25.8 DEG C, and bottom temperature is 120 DEG C.Four absorption tower 4 of carbon uses low pressure (pressure 0.4MPaG, temperature
Degree is 152 DEG C) steam heating.By liquid phase material (i.e. four absorbent of the rich carbon) supply from four absorption tower of carbon, 4 tower reactor to carbon four
The processing of desorber 5, by the gaseous phase materials from four absorption tower of carbon, 4 tower top, (gaseous phase materials are mainly unabsorbed methane, hydrogen
Body) it supplies to naphtha scrubber 7.
Liquid phase material from four absorption tower of carbon, 4 tower reactor is supplied by pressure difference to four desorber of carbon, 5 middle part.Four desorber of carbon
5 number of theoretical plate is 40, operating pressure 2.1MPaG, and tower top temperature is 40 DEG C, and bottom temperature is 122 DEG C.Four desorber 5 of carbon
Low pressure (pressure 0.4MPaG, temperature are 152 DEG C) steam heating, four desorber of carbon, 5 tower top is used to obtain rich ethane gas product,
And the liquid phase material (i.e. poor four absorbent of carbon) from four desorber of carbon, 5 tower reactor is returned after four cooler 6 of carbon is cooled to 15 DEG C
It is back to the recycling of four absorption tower 4 of carbon, while introducing fresh refinery's normal butane in the liquid phase material of four desorber of carbon, 5 tower reactor
Supply is to four absorption tower 4 of carbon as supplement.
Gaseous phase materials from four absorption tower of carbon, 4 tower top are supplied by pressure difference to 7 bottom of naphtha scrubber, are sprayed with from tower top
The oil refinery gasoline (flow 8t/h) as gasoline absorbent entered contacts.Wherein, the number of theoretical plate of naphtha scrubber is 20, operation
Pressure is 3.5MPaG, and tower top temperature is 25 DEG C, and bottom temperature is 46 DEG C.It will be supplied from the liquid phase material of 7 tower reactor of naphtha scrubber
To-stabilising arrangement separation C-4-fraction and gasoline fraction is absorbed to oil plant, recycle, and 7 tower of naphtha scrubber will be come from
The unabsorbed methane, hydrogen body on top is supplied to fuel gas pipe network.It is (rich that the composition of isolated rich ethane gas product is shown in Table 2
Remaining ingredient is impurity, such as nitrogen, carbon monoxide in ethane gas, is not shown), supply is to ethylene plant as pyrolysis furnace raw material.
In the method for the present embodiment, ethylene molar content, four absorbent internal circulating load of carbon, four absorbing tower of carbon in rich ethane gas
Kettle reboiler and four desorber tower reactor reboiler total load of carbon are referring to table 6.Ethane recovery is 92.21%.
Table 2
| Rich ethane gas | |
| Temperature, DEG C | 15.0 |
| Pressure, MPaG | 2.0 |
| Mass flow, t/h | 4.8 |
| Composition, mol% | |
| H2O | 0.06 |
| H2 | 0.00 |
| CH4 | 3.42 |
| C2H6 | 82.58 |
| C2H4 | 0.23 |
| C3H8 | 10.01 |
| C4H10 | 2.55 |
Embodiment 2
The method that the present embodiment is used to illustrate the separation coking dry gas of the present invention.
The coking dry gas that pressure from refinery's delayed coking unit is 0.6MPaG is supplied to residue gas compressor 1, is passed through
Three sections of compression processings improve dry gas pressure to 3MPaG.Then dry gas after supercharged is supplied to hydrogenation reactor 2, and adds hydrogen
Catalyst n i series catalysts (being purchased from Sinopec Beijing Research Institute of Chemical Industry, model YN-1) contact hair
Raw catalytic hydrogenation reaction, controlling reaction temperature are 220 DEG C, reaction pressure 3MPaG, volume space velocity 500h-1, hydrogenation reactor
Ethylene molar content is down to 0.1% in 2 exit gas.Then the exit gas of hydrogenation reactor 2 is used into bromine through dry gas cooler 3
Change 7 DEG C of standby cold water of lithium-absorbing formula refrigeration mechanism and be cooled to 10 DEG C, and supplies to the middle part on four absorption tower 4 of carbon.
In four absorption tower 4 of carbon, uses refinery's normal butane as four absorbent (flow 26t/h) of carbon, absorbed from carbon four
The tower top of tower 4 sprays into and dry gas counter current contacting.Wherein, the number of theoretical plate on four absorption tower 4 of carbon is 50, operating pressure 3MPaG, tower
It is 30 DEG C to push up temperature, and bottom temperature is 110 DEG C.Four absorption tower 4 of carbon uses low pressure (pressure 0.4MPaG, temperature are 152 DEG C) to steam
Vapour heats.Liquid phase material (i.e. four absorbent of rich carbon) supply to four desorber 5 of carbon from four absorption tower of carbon, 4 tower reactor is handled,
By gaseous phase materials (gaseous phase materials are mainly unabsorbed methane, hydrogen body) supply from four absorption tower of carbon, 4 tower top to gasoline
Absorption tower 7.
Liquid phase material from four absorption tower of carbon, 4 tower reactor is supplied by pressure difference to four desorber of carbon, 5 middle part.Four desorber of carbon
5 number of theoretical plate is 50, operating pressure 1.5MPaG, and tower top temperature is 70 DEG C, and bottom temperature is 110 DEG C.Four desorber 5 of carbon
Low pressure (pressure 0.4MPaG, temperature are 152 DEG C) steam heating, four desorber of carbon, 5 tower top is used to obtain rich ethane gas product,
And the liquid phase material (i.e. poor four absorbent of carbon) from four desorber of carbon, 5 tower reactor is returned after four cooler 6 of carbon is cooled to 10 DEG C
It is back to the recycling of four absorption tower 4 of carbon, while introducing fresh refinery's normal butane in the liquid phase material of four desorber of carbon, 5 tower reactor
Supply is to four absorption tower 4 of carbon as supplement.
Gaseous phase materials from four absorption tower of carbon, 4 tower top are supplied by pressure difference to 7 bottom of naphtha scrubber, are sprayed with from tower top
The refinery's naphtha (flow 8t/h) as gasoline absorbent entered contacts.Wherein, the number of theoretical plate of naphtha scrubber is 25, behaviour
It is 2.7MPaG to make pressure, and tower top temperature is 26 DEG C, and bottom temperature is 45 DEG C.By the liquid phase material from 7 tower reactor of naphtha scrubber
Supply recycles, and will come from naphtha scrubber 7 to oil plant absorption-stabilising arrangement separation C-4-fraction and gasoline fraction
The unabsorbed methane, hydrogen body of tower top is supplied to fuel gas pipe network.The composition of isolated rich ethane gas product is shown in Table 3
(remaining ingredient is impurity, such as nitrogen, carbon monoxide in rich ethane gas, is not shown), supply to ethylene plant is as pyrolysis furnace original
Material.
In the method for the present embodiment, ethane recovery 91.93%.
Table 3
| Rich ethane gas | |
| Temperature, DEG C | 15 |
| Pressure, MPaG | 1.5 |
| Mass flow, t/h | 4.4 |
| Composition, mol% | |
| H2O | 0.05 |
| H2 | 0.00 |
| CH4 | 3.81 |
| C2H6 | 79.58 |
| C2H4 | 0.22 |
| C3H8 | 9.66 |
| C4H10 | 6.67 |
Embodiment 3
The method that the present embodiment is used to illustrate the separation coking dry gas of the present invention.
The coking dry gas that pressure from refinery's delayed coking unit is 0.6MPaG is supplied to residue gas compressor 1, is passed through
Three sections of compression processings improve dry gas pressure to 5MPaG.Then dry gas after supercharged is supplied to hydrogenation reactor 2, and adds hydrogen
Catalyst n i series catalysts (being purchased from Sinopec Beijing Research Institute of Chemical Industry, model YN-S) contact hair
Raw catalytic hydrogenation reaction, controlling reaction temperature are 150 DEG C, reaction pressure 5MPaG, volume space velocity 400h-1, hydrogenation reactor
Ethylene molar content is down to 0.1% in 2 exit gas.Then the exit gas of hydrogenation reactor 2 is used into bromine through dry gas cooler 3
Change 7 DEG C of standby cold water of lithium-absorbing formula refrigeration mechanism and be cooled to 15 DEG C, and supplies to the middle part on four absorption tower 4 of carbon.
In four absorption tower 4 of carbon, uses refinery's normal butane as four absorbent (flow 18t/h) of carbon, absorbed from carbon four
The tower top of tower 4 sprays into and dry gas counter current contacting.Wherein, the number of theoretical plate on four absorption tower 4 of carbon be 25, operating pressure 4.6MPaG,
Tower top temperature is 30 DEG C, and bottom temperature is 130 DEG C.Four absorption tower 4 of carbon uses low pressure (pressure 0.4MPaG, temperature are 152 DEG C)
Steam heats.At liquid phase material (i.e. four absorbent of rich carbon) supply to four desorber 5 of carbon from four absorption tower of carbon, 4 tower reactor
Reason, extremely by gaseous phase materials (gaseous phase materials are mainly unabsorbed methane, hydrogen body) supply from four absorption tower of carbon, 4 tower top
Naphtha scrubber 7.
Liquid phase material from four absorption tower of carbon, 4 tower reactor is supplied by pressure difference to four desorber of carbon, 5 middle part.Four desorber of carbon
5 number of theoretical plate is 25, operating pressure 2.8MPaG, and tower top temperature is 70 DEG C, and bottom temperature is 138 DEG C.Four desorber 5 of carbon
Low pressure (pressure 0.4MPaG, temperature are 152 DEG C) steam heating, four desorber of carbon, 5 tower top is used to obtain rich ethane gas product,
And the liquid phase material (i.e. poor four absorbent of carbon) from four desorber of carbon, 5 tower reactor is returned after four cooler 6 of carbon is cooled to 15 DEG C
It is back to the recycling of four absorption tower 4 of carbon, while introducing fresh refinery's normal butane in the liquid phase material of four desorber of carbon, 5 tower reactor
Supply is to four absorption tower 4 of carbon as supplement.
Gaseous phase materials from four absorption tower of carbon, 4 tower top are supplied by pressure difference to 7 bottom of naphtha scrubber, are sprayed with from tower top
The refinery's heavy naphtha (flow 8t/h) as gasoline absorbent entered contacts.Wherein, the number of theoretical plate of naphtha scrubber is 15,
Operating pressure is 4.4MPaG, and tower top temperature is 25 DEG C, and bottom temperature is 50 DEG C.By the liquid phase object from 7 tower reactor of naphtha scrubber
Material supply recycles, and will come from naphtha scrubber to oil plant absorption-stabilising arrangement separation C-4-fraction and gasoline fraction
The unabsorbed methane, hydrogen body of 7 tower tops is supplied to fuel gas pipe network.The composition of isolated rich ethane gas product is shown in Table 4
(remaining ingredient is impurity, such as nitrogen, carbon monoxide in rich ethane gas, is not shown), supply to ethylene plant is as pyrolysis furnace original
Material.
In the method for the present embodiment, ethane recovery 90.78%.
Table 4
| Rich ethane gas | |
| Temperature, DEG C | 25 |
| Pressure, MPaG | 2.8 |
| Mass flow, t/h | 4.1 |
| Composition, mol% | |
| H2O | 0.06 |
| H2 | 0.00 |
| CH4 | 3.12 |
| C2H6 | 83.93 |
| C2H4 | 0.23 |
| C3H8 | 9.91 |
| C4H10 | 2.74 |
Comparative example 1
According to the method for embodiment 1, the difference is that, coking dry gas is after the supercharging of residue gas compressor 1, without catalytic hydrogenation
It handles but directly carries out cooling treatment.The composition of isolated rich ethane gas product is shown in Table 5 (remaining ingredient in rich ethane gas
It for impurity, such as nitrogen, carbon monoxide, is not shown).
Table 5
| Rich ethane gas | |
| Temperature, DEG C | 15 |
| Pressure, MPaG | 2.1 |
| Mass flow, t/h | 4.49 |
| Composition, mol% | |
| H2O | 0.06 |
| H2 | 0.00 |
| CH4 | 3.92 |
| C2H6 | 76.05 |
| C2H4 | 7.13 |
| C3H8 | 9.64 |
| C4H10 | 3.13 |
In the method for this comparative example, ethylene molar content, four absorbent internal circulating load of carbon, four absorbing tower of carbon in rich ethane gas
Kettle reboiler and four desorber tower reactor reboiler total load of carbon are referring to table 6.Ethane recovery is 92.20%.
Table 6
As known from Table 6, the method for separation coking dry gas of the invention can effectively reduce by four absorbent internal circulating load of carbon and shallow
The energy consumption of cold oil absorption plant has the characteristics that investment is small, low energy consumption, four absorbent internal circulating load of carbon is small.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of method of separation coking dry gas, which is characterized in that this method includes：Coking dry gas is subjected to catalytic hydrogenation successively
Processing, cooling treatment and four absorbent absorption of carbon processing, the gaseous phase materials and liquid for then handling four absorbent absorption of carbon
Phase materials carry out gasoline absorbent and absorb processing and four desorption of carbon processing, the gas gas-phase objects that recycling four desorption of carbon is handled respectively
Material, and the liquid phase material that four desorption of carbon is handled is back to four absorbent absorption of carbon processing.
2. according to the method described in claim 1, wherein, the method for the catalytic hydrogenation treatment includes：By coking dry gas and add
Hydrogen catalyst contacts, and temperature is 60-300 DEG C；Pressure is 1-5MPaG；Volume space velocity is 50-1000h-1。
3. according to the method described in claim 2, wherein, the temperature that coking dry gas is contacted with hydrogenation catalyst is 150-220
℃。
4. according to the method described in claim 2, wherein, the pressure that coking dry gas is contacted with hydrogenation catalyst is 3-4MPaG.
5. according to the method described in claim 2, wherein, the volume space velocity that coking dry gas is contacted with hydrogenation catalyst is 100-
500h-1。
6. according to the method described in claim 2, wherein, the hydrogenation catalyst be containing in Co, Mo, Ni and W system metal extremely
A kind of few hydrogenation catalyst of metal.
7. according to the method described in claim 6, wherein, the hydrogenation catalyst is Co-Mo-Ni series hydrocatalysts.
8. according to the method described in claim 1, wherein, this method further include before catalytic hydrogenation treatment, by coking dry gas into
Row compression processing is improving the pressure of coking dry gas to 3-5MPaG.
9. according to the method described in claim 8, wherein, the compression processing is multi-stage compression processing.
10. according to the method described in claim 9, wherein, the compression processing is three sections of compression processings.
11. according to the method described in claim 1, wherein, the condition of the cooling treatment includes：Catalytic hydrogenation treatment is obtained
Material be cooled to 5-15 DEG C.
12. according to the method for claim 11, wherein the refrigerant that cooling treatment uses is lithium-bromide absorption-type refrigerating machine
The cold water of preparation.
13. according to the method described in claim 1, wherein, the liquid phase material that four desorption of carbon is handled is cooled to 5-15 DEG C
After be back to four absorbent absorption of carbon processing.
14. according to the method described in claim 1, wherein, the method that four absorbent of the carbon absorbs processing includes：At cooling
It manages obtained material to supply to making it contact with four absorbent of carbon in four absorption tower of carbon, the number of theoretical plate on four absorption tower of carbon is 25-
50, operating pressure 3-4.6MPaG, tower top temperature are 10-30 DEG C, and bottom temperature is 100-160 DEG C.
15. according to the method for claim 14, wherein when carrying out the absorption processing of four absorbent of carbon, to four absorption tower of carbon
Interior fresh four absorbent of carbon of supplement.
16. according to the method described in any one of claim 1-15, wherein four absorbent of carbon is to contain carbon from refinery
The material of four fractions.
17. according to the method for claim 16, wherein four absorbent of carbon is the normal butane from refinery.
18. according to the method described in claim 1, wherein, the method for the desorption processing of the carbon four includes：Four absorbent of carbon is inhaled
The liquid phase material that receipts are handled is supplied to four desorber of carbon, and the number of theoretical plate of four desorber of carbon is 20-50, and operating pressure is
1.5-2.8MPaG, tower top temperature are 15-70 DEG C, and bottom temperature is 110-200 DEG C.
19. according to the method described in claim 1, wherein, the method that the gasoline absorbent absorbs processing includes：Carbon four is inhaled
The gaseous phase materials that handle of agent absorption are received to supply to making it contact with gasoline absorbent in naphtha scrubber, naphtha scrubber
Number of theoretical plate is 15-25, and operating pressure 2.7-4.5MPaG, tower top temperature is 10-40 DEG C, and bottom temperature is 20-60 DEG C.
20. according to the method for claim 19, wherein gasoline absorbent is gasoline, naphtha and scheelite from refinery
It is one or more in cerebrol.
21. according to the method described in claim 1, wherein, this method further includes：The gas that gasoline absorbent absorption is handled
Phase materials are supplied to fuel gas storage element, and the liquid phase material that gasoline absorbent absorption is handled carries out separating treatment to return
Receive four absorbent of carbon and gasoline.
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| CN103087772A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Device and method for separating refinery dry gas through oil absorption |
| CN103450941A (en) * | 2012-05-30 | 2013-12-18 | 中国石油化工股份有限公司 | Method for producing ethylene cracking raw material from coking dry gas |
| CN104557386A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Refinery mixed dry gas recovery system and recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103087772A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Device and method for separating refinery dry gas through oil absorption |
| CN103450941A (en) * | 2012-05-30 | 2013-12-18 | 中国石油化工股份有限公司 | Method for producing ethylene cracking raw material from coking dry gas |
| CN104557386A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Refinery mixed dry gas recovery system and recovery method |
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