CN109574780A - A kind of system and method for oil refinery dry gas ethylbenzene - Google Patents
A kind of system and method for oil refinery dry gas ethylbenzene Download PDFInfo
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- CN109574780A CN109574780A CN201910058008.6A CN201910058008A CN109574780A CN 109574780 A CN109574780 A CN 109574780A CN 201910058008 A CN201910058008 A CN 201910058008A CN 109574780 A CN109574780 A CN 109574780A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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Abstract
The invention belongs to petrochemical industry more particularly to a kind of system and method for oil refinery dry gas ethylbenzene.System provided by the invention includes: water scrubber；The absorption deammoniation tower being connected is exported with the dry gas of water scrubber, adsorbs in deammoniation tower and is filled with sour modified activated carbon；The ethylbenzene reaction tower processed being connected is exported with the dry gas of absorption deammoniation tower；The benzene transfer pipeline being connected with the benzene feed inlet of ethylbenzene reaction tower processed.In system provided by the invention, oil refinery dry gas followed by water scrubber, adsorb deammoniation tower and ethylbenzene reaction tower processed, be made ethylbenzene.System provided by the invention between water scrubber and ethylbenzene reaction tower processed by being filled with the absorption deammoniation tower of particular adsorbent, significantly reduce the ammonia content into ethylbenzene reaction tower dry gas processed, to delay the speed of ethylbenzene reaction tower catalyst inactivation processed caused by existing as ammonia, the service life for extending ethylbenzene catalyst processed ensure that the even running of ethylbenzene system processed.
Description
Technical field
The invention belongs to petrochemical industry more particularly to a kind of system and method for oil refinery dry gas ethylbenzene.
Background technique
Oil refinery dry gas refers to the noncondensable gas (also referred to as distillation gas) for generating and recycling in oil plant oil refining process, wherein containing
There is a large amount of ethylene, prepares raw material frequently as other chemicals.
Currently, preparing ethylbenzene in the main application direction of oil refinery dry gas and being most widely used, in solid acid catalysis
In the presence of agent, benzene reacts in the reactor with the ethylene in dry gas generates ethylbenzene.But due to containing micro nitrogen, meeting in petroleum
Cause in the dry gas generated can containing a small amount of ammonia, and ammonia can occur with solid acid catalyst it is irreversible react, cause to urge
Agent inactivation, to cause the reduction of catalyst service life.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of system and method for oil refinery dry gas ethylbenzene, the present invention is mentioned
The system of confession can improve dry gas quality, extend ethylbenzene catalyst service life processed, guarantee the even running of system.
The present invention provides a kind of systems of oil refinery dry gas ethylbenzene, comprising:
Water scrubber；
The absorption deammoniation tower being connected is exported with the dry gas of the water scrubber, the modified work of acid is filled in the absorption deammoniation tower
Property charcoal；
The ethylbenzene reaction tower processed being connected is exported with the dry gas of the absorption deammoniation tower；
The benzene transfer pipeline being connected with the benzene feed inlet of the ethylbenzene reaction tower processed.
Preferably, the sour modified activated carbon is prepared in accordance with the following methods:
Acid solution is impregnated into active carbon, is dried later, and sour modified activated carbon is obtained.
Preferably, one of sulfuric acid, hydrochloric acid, nitric acid, citric acid and acetic acid or a variety of are contained in the acid solution.
Preferably, the mode of the dipping is that active carbon is dipped into acid solution.
Preferably, the concentration of the acid solution is 10~80wt%；
The time of the immersion is 24~48h.
Preferably, the dry gas air inlet for adsorbing the loadings of sour modified activated carbon and the absorption deammoniation tower in deammoniation tower
The ratio of amount is (1~2) kg:1kg/h.
It preferably, further include surge tank, the dry gas outlet of the surge tank is connected with the dry gas import of the water scrubber.
It preferably, further include rectifying column, the feed inlet of the rectifying column is connected with the discharge port of the ethylbenzene reaction tower processed.
It preferably, further include heating furnace, the heating furnace is arranged on the benzene transfer pipeline, for benzene transfer pipeline
The benzene of middle conveying is heated.
The present invention provides a kind of methods of oil refinery dry gas ethylbenzene, comprising the following steps:
A) deamination is successively washed and adsorbed to oil refinery dry gas, obtains deamination dry gas；
The adsorbent of the absorption deamination includes sour modified activated carbon；
B) in the presence of a catalyst, the deamination dry gas and benzene hybrid reaction, obtain ethylbenzene.
Compared with prior art, the present invention provides a kind of system and method for oil refinery dry gas ethylbenzene.The present invention provides
System include: water scrubber；The absorption deammoniation tower being connected is exported with the dry gas of the water scrubber, is loaded in the absorption deammoniation tower
There is sour modified activated carbon；The ethylbenzene reaction tower processed being connected is exported with the dry gas of the absorption deammoniation tower；With it is anti-with the ethylbenzene processed
The benzene transfer pipeline for answering the benzene feed inlet of tower connected.In system provided by the invention, oil refinery dry gas first in water scrubber into
Row washing deamination, remaining a small amount of ammonia is again in absorption deammoniation tower by sour modified activated carbon adsorbing and removing in dry gas later, most
The dry gas after deamination obtains ethylbenzene with benzene hybrid reaction in ethylbenzene reaction tower processed afterwards.System provided by the invention passes through in water
The absorption deammoniation tower for being filled with particular adsorbent between tower and ethylbenzene reaction tower processed is washed, is significantly reduced anti-into ethylbenzene processed
The ammonia content of tower dry gas is answered, to delay the speed of ethylbenzene reaction tower catalyst inactivation processed caused by existing as ammonia, is prolonged
The service life for having grown ethylbenzene catalyst processed ensure that the even running of ethylbenzene system processed.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the system flow chart of oil refinery dry gas ethylbenzene provided in an embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of systems of oil refinery dry gas ethylbenzene, comprising:
Water scrubber；
The absorption deammoniation tower being connected is exported with the dry gas of the water scrubber, the modified work of acid is filled in the absorption deammoniation tower
Property charcoal；
The ethylbenzene reaction tower processed being connected is exported with the dry gas of the absorption deammoniation tower；
The benzene transfer pipeline being connected with the benzene feed inlet of the ethylbenzene reaction tower processed.
It is the system flow chart of oil refinery dry gas ethylbenzene provided in an embodiment of the present invention referring to Fig. 1, Fig. 1,1 is slow in Fig. 1
Rush tank, 2 be water scrubber, 2-1 be water scrubber circulating pump, 3 be absorption deammoniation tower, 4 be ethylbenzene reaction tower processed, 5 be benzene transfer pipeline,
6 be heating furnace.
Oil refinery dry gas ethylbenzene system provided by the invention includes water scrubber 2, absorption deammoniation tower 3,4 and of ethylbenzene reaction tower processed
Benzene transfer pipeline 5.Wherein, water scrubber 2 is for washing oil refinery dry gas, to remove ammonia in dry gas, be provided with into
The mouth of a river, dry gas import and dry gas outlet.In one embodiment provided by the invention, water scrubber 2 is spray column, the spray column
Internal diameter be 1000~1500mm, concretely 1000mm, 1050mm, 1100mm, 1150mm, 1200mm, 1250mm,
1300mm, 1350mm, 1400mm, 1450mm or 1500mm；The tower height of the spray column is 12000~20000mm, concretely
12000mm、12500mm、13000mm、13500mm、14000mm、14500mm、15000mm、15500mm、16000mm、
16514mm, 17000mm, 17500mm, 18000mm, 18500mm, 19000mm, 19500mm or 20000mm.It is provided in the present invention
A water scrubber 2 be spray column embodiment in, the bottom of water scrubber 2 is also connected with water scrubber circulating pump 2-1, and water scrubber follows
The outlet end of ring pump 2-1 is connected with the spray head of 2 inner cavity top of water scrubber.It is in another water scrubber 2 provided by the invention
In the embodiment of spray column, it is additionally provided with packing layer between the dry gas import of the spray head and water scrubber 2 of water scrubber 2, it is described to fill out
The highly preferred of the bed of material is 2000~6000mm, concretely 2000mm, 2500mm, 3000mm, 3500mm, 4000mm,
4500mm, 5000mm, 5500mm or 6000mm；The filler of described filler layer filling is preferably 250Y structured packing.
In the present invention, absorption deammoniation tower 3 is used to carry out adsorbing and removing to a small amount of ammonia remaining in dry gas after washing,
On be provided with dry gas import and dry gas outlet, the dry gas for adsorbing dry gas import and the water scrubber 2 of deammoniation tower 3, which exports, to be connected.At this
It invents in the one embodiment provided, in tower top, dry gas outlet is arranged in tower bottom for the dry gas import setting of absorption deammoniation tower 3.?
It in the present invention, adsorbs and is filled with sour modified activated carbon in deammoniation tower 3, the acid modified activated carbon can be prepared in accordance with the following methods
It obtains:
Acid solution is impregnated into active carbon, is dried later, and sour modified activated carbon is obtained.
In the preparation method of above-mentioned sour modified activated carbon provided by the invention, sulfuric acid, salt are preferably comprised in the acid solution
One of acid, nitric acid, citric acid and acetic acid are a variety of, further preferably two or three in sulfuric acid, citric acid and acetic acid.
In the embodiment that an acid solution provided by the invention contains sulfuric acid and citric acid, the mass ratio of the sulfuric acid and citric acid
Preferably (0.5~2): 1, concretely 0.5:1,1:1,1.5:1 or 2:1.Contain in an acid solution provided by the invention
In the embodiment of citric acid and acetic acid, the mass ratio of the citric acid and acetic acid is preferably 1:(0.5~2), concretely 1:
0.5,1:1,1:1.5 or 1:2.In the embodiment of the one provided by the invention acid solution sulfur acid, citric acid and acetic acid, institute
The mass ratio for stating sulfuric acid, citric acid and acetic acid is preferably (0.5~2): 1 (0.5~2), more preferably (0.5~1): 1:(1.5~
2)。
In the preparation method of above-mentioned sour modified activated carbon provided by the invention, the mode of the dipping preferably will be active
Charcoal is dipped into acid solution；The concentration of the acid solution is preferably 10~80wt%, concretely 10wt%, 15wt%, 20wt%,
25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%
Or 80wt%；The time of the immersion is preferably 24~48h, concretely for 24 hours, 25h, 26h, 27h, 28h, 29h, 30h, 31h,
32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h or 48h.
In the preparation method of above-mentioned sour modified activated carbon provided by the invention, the mode of the drying is preferably dried；
The temperature of the drying is preferably 200~350 DEG C concretely 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 230
℃、235℃、240℃、245℃、250℃、255℃、260℃、265℃、270℃、275℃、280℃、285℃、290℃、
295 DEG C, 300 DEG C, 305 DEG C, 310 DEG C, 315 DEG C, 320 DEG C, 325 DEG C, 330 DEG C, 335 DEG C, 340 DEG C, 345 DEG C or 350 DEG C；It is described
The dry time be preferably 12~48h concretely 12h, 16h, 20h, for 24 hours, 28h, 32h, 36h, 40h, 44h or 48h.
In the present invention, absorption the highly preferred of deammoniation tower 3 be 10000~15000mm, concretely 10000mm,
10500mm、11000mm、11500mm、12000mm、12500mm、13000mm、13500mm、13700mm、14000mm、
14500mm or 15000mm；It adsorbs in deammoniation tower 3, the highly preferred filling of sour modified activated carbon is 2000~10000mm, specifically
Can for 2000mm, 2500mm, 3000mm, 3500mm, 4000mm, 4500mm, 5000mm, 5500mm, 6000mm, 6500mm,
7000mm, 7500mm, 8000mm, 8500mm, 9000mm, 9500mm or 10000mm.In the present invention, the sour modified active
Charcoal preferably divides 2~3 layers of filling, and the spacing of adjacent two layers acid modified active layer of charcoal is preferably 500~1500mm, concretely
500mm, 600mm, 700mm, 800mm, 900mm, 1000mm, 1100mm, 1200mm, 1300mm, 1400mm or 1500mm.
In the present invention, when the system is run, the loadings of sour modified activated carbon and absorption deamination in deammoniation tower 3 are adsorbed
The ratio of the dry gas air inflow of tower 3 is preferably (1~2) kg:1kg/h, concretely 1kg:1kg/h, 1.2kg:1kg/h, 1.5kg:
1kg/h, 1.7kg:1kg/h or 2kg:1kg/h.
In the present invention, ethylbenzene reaction tower 4 processed is reacted for carrying out dry gas with the mixed catalytic of benzene, is provided with dry gas
Import, benzene inlet port and outlet port are filled with ethylbenzene catalyst processed, the dry gas import and absorption of ethylbenzene reaction tower 4 processed in inner cavity
The dry gas outlet of deammoniation tower 3 is connected.In one embodiment provided by the invention, the dry gas import of ethylbenzene reaction tower 4 processed is arranged
In tower side wall, the setting of benzene feed inlet is arranged in tower top, discharge port in tower bottom.In the present invention, the internal diameter of ethylbenzene reaction tower 4 processed is excellent
Be selected as 1200~2500mm, concretely 1200mm, 1250mm, 1300mm, 1350mm, 1400mm, 1450mm, 1500mm,
1550mm、1600mm、1650mm、1700mm、1750mm、1800mm、1850mm、1900mm、1950mm、2000mm、2050mm、
2100mm, 2150mm, 2200mm, 2250mm, 2300mm, 2350mm, 2400mm, 2450mm or 2500mm；Ethylbenzene reaction tower 4 processed
It is highly preferred be 15000~25000mm, concretely 15000mm, 15500mm, 16000mm, 16500mm, 17022mm,
17500mm、18000mm、18500mm、19000mm、19500mm、20000mm、20500mm、21000mm、21500mm、
22000mm, 22500mm, 23000mm, 23500mm, 24000mm, 24500mm or 25000mm.In the present invention, the ethylbenzene
Catalyst preferably divides 3~8 layers of filling, and highly preferred every layer of filling is 300~1000mm, concretely 300mm, 350mm,
400mm, 450mm, 500mm, 550mm, 600mm, 650mm, 700mm, 750mm, 800mm, 850mm, 900mm, 950mm or
1000mm；Every layer of ethylbenzene loaded catalyst is preferably 500~1500kg, concretely 500kg, 550kg, 600kg,
650kg、700kg、750kg、800kg、850kg、900kg、950kg、1000kg、1050kg、1100kg、1150kg、1200kg、
1250kg, 1300kg, 1350kg, 1400kg, 1450kg or 1500kg；The spacing of adjacent two layers ethylbenzene catalyst layer is preferably
2000~6000mm, concretely 2000mm, 2500mm, 3000mm, 3500mm, 4000mm, 4500mm, 5000mm, 5500mm
Or 6000mm.
In the present invention, benzene transfer pipeline 5 is connected with the benzene feed inlet of ethylbenzene reaction tower 4, for benzene to be transported to second processed
In benzene reaction tower 4.
In the present invention, it is also preferable to include surge tanks 1 for the system, for stablizing the dry gas pressure into water scrubber 2, thereon
It is provided with dry gas import and dry gas outlet, the dry gas outlet of surge tank 1 is connected with the dry gas import of water scrubber 2.
In the present invention, it is also preferable to include rectifying columns for the system, anti-containing ethylbenzene for preparing to ethylbenzene reaction tower processed
Answer product to carry out rectifying separation, obtain high purity ethylbenzene, be provided with feed inlet and ethylbenzene discharge port, the rectifying column into
Material mouth is connected with the discharge port of ethylbenzene reaction tower 4 processed.
In the present invention, it is also preferable to include heating furnaces 6, heating furnace 6 to be arranged on the benzene transfer pipeline 5 for the system,
For being heated to the benzene conveyed in benzene transfer pipeline.
In system provided by the invention, oil refinery dry gas carries out washing deamination first in water scrubber, residual in dry gas later
For a small amount of ammonia stayed again in absorption deammoniation tower by sour modified activated carbon adsorbing and removing, the dry gas after last deamination is anti-in ethylbenzene processed
Ying Tazhong and benzene hybrid reaction, obtain ethylbenzene.
System provided by the invention is by being filled with particular adsorbent between water scrubber and ethylbenzene reaction tower processed
Deammoniation tower is adsorbed, the ammonia content into ethylbenzene reaction tower dry gas processed is significantly reduced, to delay to cause since ammonia exists
Ethylbenzene reaction tower catalyst inactivation processed speed, extend ethylbenzene catalyst service life processed, ensure that ethylbenzene system processed
Even running.
The present invention also provides a kind of methods of oil refinery dry gas ethylbenzene, comprising the following steps:
A) deamination is successively washed and adsorbed to oil refinery dry gas, obtains deamination dry gas；
The adsorbent of the absorption deamination includes sour modified activated carbon；
B) in the presence of a catalyst, the deamination dry gas and benzene hybrid reaction, obtain ethylbenzene.
In method provided by the invention, oil refinery dry gas is washed first.Wherein, the oil refinery dry gas is petroleum cracking
What is generated contains ethylene gas, can also be containing a small amount of in oil refinery dry gas due to can also contain micro nitrogen in petroleum
Ammonia.In one embodiment provided by the invention, the volume of ethylene content in the oil refinery dry gas is preferably 10~15%, tool
Body can be 10%, 11%, 12%, 13%, 14% or 15%；Ammonia level in the oil refinery dry gas is preferably 100~
300ppm, concretely 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 158ppm, 160ppm,
170ppm, 180ppm, 190ppm, 196ppm, 200ppm, 210ppm, 220ppm, 230ppm, 240ppm, 250ppm or
300ppm.In the present invention, the oil refinery dry gas is before being washed, the preferably first steady pressure in surge tank.In this hair
In bright, the washing carries out preferably in water scrubber, carries out in the water scrubber 2 being more preferably described above, and the refinery is dry
Residence time of the gas in water scrubber is preferably 5~30s, concretely 5s, 8s, 10s, 12s, 15s, 17s, 20s, 23s, 25s,
27s or 30s.In the present invention, the oil refinery dry gas amount and it is described washing water ratio be preferably 10135kg/h:(4000~
7000) kg/h, concretely 10135kg/h:4000kg/h, 10135kg/h:4500kg/h, 10135kg/h:5000kg/h,
10135kg/h:5500kg/h, 10135kg/h:6000kg/h, 10135kg/h:6500kg/h or 10135kg/h:7000kg/h.
In an embodiment washed in water scrubber provided by the invention, the washing water is by water scrubber rate of water make-up and water
Wash tower quantity of circulating water to form, the flow-rate ratio of the rate of water make-up and quantity of circulating water is preferably 2000:(2000~5000), concretely
2000:2000,2000:2500,2000:3000,2000:3500,2000:4000,2000:4500 or 2000:5000.
In method provided by the invention, oil refinery dry gas carries out absorption deamination after washing.Wherein, the absorption is de-
The adsorbent of ammonia includes sour modified activated carbon, and the acid modified activated carbon hereinbefore by the agency of, details are not described herein.At this
In invention, the absorption deamination preferably absorption deammoniation tower in carry out, in the absorption deammoniation tower 3 being more preferably described above into
Row, air speed of the dry gas in the absorption deammoniation tower is preferably 0.4~0.8h-1, concretely 0.4h-1、0.45h-1、0.5h-1、
0.55h-1、0.6h-1、0.65h-1、0.7h-1、0.75h-1Or 0.8h-1.Dry gas obtains deamination dry gas after adsorbing deamination.
In method provided by the invention, after obtaining deamination dry gas, in the presence of a catalyst, the deamination dry gas and benzene are mixed
Close reaction.Wherein, the catalyst be solid acid catalyst include but is not limited to SEB-08 ethylbenzene alkylation catalyst and/or
DL0801 ethylbenzene alkylation catalyst；The molar ratio of the benzene and the ethylene in the deamination dry gas is preferably (6~9): 1, tool
Body can be 6:1,6.5:1,7:1,7.5:1,8:1,8.5:1 or 9:1；The temperature of the hybrid reaction is preferably 330~380 DEG C,
Concretely 330 DEG C, 335 DEG C, 340 DEG C, 345 DEG C, 350 DEG C, 355 DEG C, 360 DEG C, 365 DEG C, 370 DEG C, 375 DEG C or 380 DEG C；Institute
The pressure for stating hybrid reaction is preferably 0.3~1MPa, concretely 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa,
0.55MPa, 0.6MPa, 0.65MPa, 0.7MPa, 0.75MPa, 0.8MPa, 0.85MPa, 0.9MPa, 0.95MPa or 1MPa.?
In the present invention, the hybrid reaction is preferably carried out in ethylbenzene reaction tower processed, the ethylbenzene processed reaction being more preferably described above
It is carried out in tower 4, in reaction process, the air speed of the ethylene in the deamination dry gas is preferably 0.2~0.5h-1, concretely 0.2h-1、0.25h-1、0.3h-1、0.35h-1、0.4h-1、0.45h-1Or 0.5h-1.After reaction, it obtains producing containing the reaction containing ethylbenzene
Object.In the present invention, it is preferred to carry out rectifying to the reaction product, the ethylbenzene of high-purity is obtained.
Method provided by the invention is substantially dropped by wash to oil refinery dry gas and adsorbing deamination using particular adsorbent
The low ammonia content of dry gas can effectively delay ethylbenzene catalytic reaction processed caused by existing during subsequent ethylbenzene processed as ammonia
The speed of agent inactivation, extends ethylbenzene catalyst service life processed, ensure that the efficiency of ethylbenzene processed.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
1) oil refinery dry gas ethylbenzene system
One kind provided in this embodiment oil refinery dry gas ethylbenzene system as shown in Figure 1, including surge tank 1, water scrubber 2,
Water scrubber circulating pump 2-1, absorption deammoniation tower 3, ethylbenzene reaction tower 4 processed, benzene transfer pipeline 5, heating furnace 6 and rectifying column are (in figure not
It draws).
In the present embodiment, dry gas import and dry gas outlet are provided on surge tank 1, the dimensions of surge tank 1 is Φ
1400 × 6660 × 10 (internal diameter × height × wall thickness, units: mm).
In the present embodiment, water scrubber 2 is filler spray column, and the specification of water scrubber 2 is that Φ 1200 × 16514 × 14 is (interior
Diameter × height × wall thickness, unit: mm), the bed stuffing height in water scrubber 2 is 4000mm, and the filler of filling is 250Y structured packing；
Water inlet, dry gas import and dry gas outlet are provided on water scrubber 2, the dry gas import of water scrubber 2 and the dry gas of surge tank 1 export
It is connected, the bottom of water scrubber 2 is also connected with water scrubber circulating pump 2-1, in the outlet end and water scrubber 2 of water scrubber circulating pump 2-1
The spray head of top of chamber is connected.
In the present embodiment, absorption deammoniation tower 3 is packed tower, and the specification of absorption deammoniation tower 3 is Φ 1800 × 13700 × 14
(internal diameter × height × wall thickness, unit: mm) is adsorbed in deammoniation tower 3 and is provided with two layers of packing layer, and the height of every layer of packing layer is
4000mm, the spacing of two layers of packing layer are 1000mm, and the filler of filling is sour modified activated carbon, and bulk density is 0.5~0.6g/
cm3；Be provided with dry gas import at the top of absorption deammoniation tower 3, bottom is provided with dry gas outlet, adsorb the dry gas import of deammoniation tower 3 with
The dry gas outlet of water scrubber 2 is connected.
In the present embodiment, the sour modified activated carbon is prepared in accordance with the following methods: active carbon is dipped into concentration
For in the citric acid solution of 40wt%, immersion is taken out afterwards for 24 hours, is dried at 200 DEG C for 24 hours, obtain sour modified activated carbon.
Wherein, the appearance of the active carbon is black bar, and technical indicator is as shown in table 1:
The technical indicator of 1 active carbon of table
| Project | Index | Unit | Analysis method |
| Intensity | ≥92 | % | GB/T7702 |
| Iodine number | ≥900 | mg/g | GB/T7702 |
| Water capacity | ≤70 | % | GB/T7702 |
| Moisture | ≤8 | % | GB/T7702 |
| Loading density | 500~600 | kg/m3 | HG/T7702 |
| Pore volume | ≥0.7 | % | HG/T7702 |
| Specific surface area | ≥950 | m2/g | HG/T7702 |
| Citric acid load capacity | > 10 | % | Parse gravimetry |
| PH value | < 5 | The amount for adding normal-temperature water is 2 times of deamidization weight, is detected in 15 seconds |
In the present embodiment, ethylbenzene reaction tower 4 processed is packed tower, and the specification of ethylbenzene reaction tower 4 is Φ 1800 × 17022
(internal diameter × height, unit: mm), is provided with five layers of packing layer in ethylbenzene reaction tower 4 processed, and the height of every layer of packing layer is 600mm, dress
The amount of filling out is 900kg, and the spacing of packing layer is 3000mm, and the filler of filling is that solid acid catalyst (urge by the alkylation of SEB-08 ethylbenzene
Agent)；Benzene feed inlet is provided at the top of ethylbenzene reaction tower 4 processed, side wall is provided with dry gas import, and bottom is provided with discharge port, system
The dry gas import of ethylbenzene reaction tower 4 is connected with the dry gas outlet of absorption deammoniation tower 3.
In the present embodiment, benzene transfer pipeline 5 is connected with the benzene feed inlet of ethylbenzene reaction tower 4, is provided with heating furnace
6。
In the present embodiment, the specification of rectifying column is Φ 2000 × 69320 × 36 (internal diameter × height × wall thickness, unit: mm),
Feed inlet and ethylbenzene discharge port, the discharge port phase of the feed inlet of the rectifying column and ethylbenzene reaction tower 4 processed are provided on rectifying column
Even.
The operational process of oil refinery dry gas ethylbenzene system provided by the embodiment are as follows: oil refinery dry gas is steady first in surge tank 1
Then constant-pressure carries out washing deamination in water scrubber 2, later in dry gas remaining a small amount of ammonia again absorption deammoniation tower 3 in
By sour modified activated carbon adsorbing and removing, then the dry gas after deamination heats and leads to by heating furnace 6 in ethylbenzene reaction tower 4 processed
The hot benzene hybrid reaction that benzene transfer pipeline 5 is transported in reaction tower is crossed, obtains the reaction product containing ethylbenzene, final reaction product exists
Rectifying is carried out in rectifying column, obtains high purity ethylbenzene.
2) system deamination effect assessment
It is 10135kg/h, water scrubber rate of water make-up 2000kg/h, washing water internal circulating load 3500kg/h in oil refinery dry gas air inflow
Operating condition under, dry gas wash it is forward and backward and absorption deamination after ammonia density it is as shown in table 2:
Ammonia content in 2 dry gas of table
| Sample | Ammonia before washing | Ammonia after washing | Ammonia after absorption deamination |
| Sample 1 | 196ppm | 15ppm | 2ppm |
| Sample 2 | 158ppm | 10ppm | 2ppm |
| Sample 3 | 210ppm | 15ppm | 3ppm |
| Sample 4 | 240ppm | 25ppm | 4ppm |
| Sample 5 | 160ppm | 15ppm | 0ppm |
It can be seen that by the data in table 1 and be only capable of ammonia concentration being down to 30ppm after washing hereinafter, again through inhaling
Then ammonia concentration can be down to 5ppm or less after attached deamination.
Embodiment 2
Influence of the various concentration ammonia to ethylbenzene processed is catalyzed
The ethylbenzene reaction tower 4 processed provided using embodiment 1 will be passed through dry gas and heat in dry gas import and benzene feed inlet respectively
Benzene, controls reaction pressure 0.6MPa, and 350 DEG C of reaction temperature, benzene alkene ratio (molar ratio) 6:1, the air speed 0.3h of the ethylene in dry gas-1, calculate the conversion of ethylene of different ammonia density dry gas.Wherein, the formula of conversion of ethylene are as follows:
Conversion of ethylene={ (A-B)/A } * 100%；
In above formula, A indicates the concentration of ethylene in dry gas, and B indicates to participate in the ethylene concentration of reaction.
Conversion of ethylene under various concentration ammonia is as shown in table 3:
Conversion of ethylene under 3 various concentration ammonia of table
It can be seen that by the data in table 2 and increased with ammonia concentration in dry gas, conversion of ethylene dramatic decrease, catalysis
Agent deactivation time is obviously shortened.
Embodiment 3
The comparison of different adsorbent absorption deamination effects
Adsorbent source is as follows:
Resin: macropore polyamide, specific surface area: 500~600m2/g；
Normal activated carbon:
The technical indicator of 4 normal activated carbon of table
| Project | Index | Unit | Analysis method |
| Intensity | ≥92 | % | GB/T7702 |
| Iodine number | ≥900 | mg/g | GB/T7702 |
| Water capacity | ≤70 | % | GB/T7702 |
| Moisture | ≤8 | % | GB/T7702 |
| Loading density | 500~600 | Kg/m3 | HG/T7702 |
| Pore volume | ≥0.7 | % | HG/T7702 |
| Specific surface area | ≥950 | m2/g | HG/T7702 |
Sour modified activated carbon: the normal activated carbon is impregnated for 24 hours in the citric acid solution that concentration is 30wt%, Zhi Hou
It is dried at 200 DEG C for 24 hours, obtains sour modified activated carbon；
Molecular sieve: type A zeolite molecular sieve, chemical formula Na2O·Al2O3·2SiO2·4.5H2O, internal aperture are 4.2
Angstrom；
Silicate: improvement palygorskite, 2.05~2.32g/cm of density3。
Experimentation: experiment dry gas is passed into the bottom of device equipped with adsorbent at 0.35MPa, adsorbent is to dry gas
The ammonia of middle carrying is adsorbed, while gas ammonia level changes after the absorption being discharged at the top of detection device, until after absorption
The ammonia level of gas is no longer changed, and calculating is passed through gas flow, the maximum ammonia amount of unit of account volume of adsorbent absorption.
Specific experimental condition and experimental result are as shown in table 5:
The different adsorbents of table 5 adsorb deamination effect
The ammonia gas absorption capacity of different adsorbents is calculated, calculation formula is as follows:
Va=V/m unit: m3·g-1
In formula, V indicates the ammonia volume of absorption, and m indicates the quality of adsorbent.
Calculated result is as shown in table 6:
The different adsorbents of table 6 remove ammonia effect
| Different adsorbents | Adsorption capacity/% |
| Resin | Essentially 0 |
| Normal activated carbon | 1.5 |
| Sour modified activated carbon | 5 |
| Molecular sieve | Essentially 0 |
| Silicate | Essentially 0 |
By the data in table 3 it is found that active carbon has preferable suction-operated to ammonia, and the modified effect of acid is obviously improved.
Embodiment 4
The comparison of different acid modified activated carbon absorption deamination effects
The experimentation of reference implementation example 3, by active carbon used in embodiment 3 in concentration in 30wt% difference acid solution
It impregnates for 24 hours, is dried at 200 DEG C compare different sour modified activated carbons for 24 hours to the adsorption effect of ammonia later.
Experimental result is as shown in table 7:
The different sour modified activated carbons of table 7 remove ammonia effect
Embodiment 5
The comparison of the modified activated carbon absorption deamination effect of different acid load capacity
The experimentation of reference implementation example 3, by taking citric acid as an example, by active carbon used in embodiment 3 in concentration difference
Citric acid 8 shown in:
The different sour modified activated carbons of table 8 remove ammonia effect
| Citric acid concentration | Adsorption capacity/% |
| 10wt% | 2 |
| 20wt% | 3 |
| 30wt% | 5 |
| 40wt% | 5.6 |
| 50wt% | 6 |
| 60wt% | 6.2 |
| 70wt% | 6.2 |
| 80wt% | 6.5 |
It can be seen that comprehensive good green deamination effect and economy by 5 data of table, use concentration for the acid of 30~50wt%
It is best that liquid handles active carbon effect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of system of oil refinery dry gas ethylbenzene, comprising:
Water scrubber；
The absorption deammoniation tower being connected is exported with the dry gas of the water scrubber, is filled with sour modified active in the absorption deammoniation tower
Charcoal；
The ethylbenzene reaction tower processed being connected is exported with the dry gas of the absorption deammoniation tower；
The benzene transfer pipeline being connected with the benzene feed inlet of the ethylbenzene reaction tower processed.
2. system according to claim 1, which is characterized in that the acid modified activated carbon is prepared into accordance with the following methods
It arrives:
Acid solution is impregnated into active carbon, is dried later, and sour modified activated carbon is obtained.
3. system according to claim 2, which is characterized in that contain sulfuric acid, hydrochloric acid, nitric acid, citric acid in the acid solution
With one of acetic acid or a variety of.
4. system according to claim 2, which is characterized in that the mode of the dipping is that active carbon is dipped into acid solution
In.
5. system according to claim 4, which is characterized in that the concentration of the acid solution is 10~80wt%；
The time of the immersion is 24~48h.
6. system according to claim 1, which is characterized in that the loadings of sour modified activated carbon in the absorption deammoniation tower
Ratio with the dry gas air inflow of the absorption deammoniation tower is (1~2) kg:1kg/h.
7. system according to claim 1, which is characterized in that further include surge tank, the outlet of the dry gas of the surge tank with
The dry gas import of the water scrubber is connected.
8. system according to claim 1, which is characterized in that it further include rectifying column, the feed inlet of the rectifying column and institute
The discharge port for stating ethylbenzene reaction tower processed is connected.
9. system according to claim 1, which is characterized in that further include heating furnace, the heating furnace is arranged in the benzene
On transfer pipeline, for being heated to the benzene conveyed in benzene transfer pipeline.
10. a kind of method of oil refinery dry gas ethylbenzene, comprising the following steps:
A) deamination is successively washed and adsorbed to oil refinery dry gas, obtains deamination dry gas；
The adsorbent of the absorption deamination includes sour modified activated carbon；
B) in the presence of a catalyst, the deamination dry gas and benzene hybrid reaction, obtain ethylbenzene.
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| CN110283035A (en) * | 2019-07-22 | 2019-09-27 | 山东京博石油化工有限公司 | A kind of processing unit and method of the raw material dry gas for ethylbenzene processed |
| CN111170819A (en) * | 2020-01-20 | 2020-05-19 | 中国石油化工股份有限公司 | Device and process for improving utilization rate of ethylene and propylene in dry gas |
| CN111450662A (en) * | 2020-05-29 | 2020-07-28 | 山东京博石油化工有限公司 | Method and device for purifying raw material dry gas for preparing ethylbenzene |
| CN112759503A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Dry gas pretreatment system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110283035A (en) * | 2019-07-22 | 2019-09-27 | 山东京博石油化工有限公司 | A kind of processing unit and method of the raw material dry gas for ethylbenzene processed |
| CN112759503A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Dry gas pretreatment system and method |
| CN112759503B (en) * | 2019-10-21 | 2023-01-31 | 中国石油化工股份有限公司 | Dry gas pretreatment system and method |
| CN111170819A (en) * | 2020-01-20 | 2020-05-19 | 中国石油化工股份有限公司 | Device and process for improving utilization rate of ethylene and propylene in dry gas |
| CN111170819B (en) * | 2020-01-20 | 2022-06-21 | 中国石油化工股份有限公司 | Device and process for improving utilization rate of ethylene and propylene in dry gas |
| CN111450662A (en) * | 2020-05-29 | 2020-07-28 | 山东京博石油化工有限公司 | Method and device for purifying raw material dry gas for preparing ethylbenzene |
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