CN106745442B - A kind of refinery basic sewage acidification reaction device and acidization tool - Google Patents
A kind of refinery basic sewage acidification reaction device and acidization tool Download PDFInfo
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- CN106745442B CN106745442B CN201510800824.1A CN201510800824A CN106745442B CN 106745442 B CN106745442 B CN 106745442B CN 201510800824 A CN201510800824 A CN 201510800824A CN 106745442 B CN106745442 B CN 106745442B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of refinery basic sewage acidification reaction device, including oil-gas mixer, air-fuel mixture tower, air-fuel mixture pump, acidification reaction tower and acidizing pump, oil-gas mixer import respectively with SO2Feed pipe is connected with finish feed pipe, and outlet is connect with air-fuel mixture tower import, successively sets fiber-film contact, collecting tank, diversion pipe in air-fuel mixture tower from top to bottom, diversion pipe bottom end is deep under tower reactor liquid level；The acidification reaction tower is telescoping structure, and inner cylinder is extraction tower, and outer cylinder is connected to acidification reaction tower tower reactor；Air-fuel mixture tower tower reactor is connected to acidification reaction tower tower reactor by overflow pipe, and the mixed liquor of air-fuel mixture tower tower reactor is overflowed in acidification reaction tower tower reactor by this overflow pipe.Acidization tool of the invention is realized using above-mentioned apparatus.The present invention can reduce the heat that acidification reaction generates while alkaline residue is acidified, and increase the hydrogen sulfide of acidification generation, the absorption efficiency of mercaptan thioether；Have the characteristics that structure is simple, degree of integration is high, occupied area is small, absorb and be acidified high-efficient.
Description
Technical field
The invention belongs to environment-protection wastewater processing technology field, relate in particular to a kind of refinery basic sewage acidification reaction device and
Acidization tool.
Background technique
In Refinery Oil alkali cleaning subtractive process, the alkaline waste liquor that can generate the object containing high density pollution is known as alkaline residue,
The discharge amount of COD, sulfide and phenol account for the 40%-50% or more of the such pollutant discharge amount of oil plant.These alkali residue waste liquids, if
Direct emission would seriously pollute the environment, and severe corrosion equipment.In recent years, as national environmental protection regulation, standard are increasingly complete
Standby and stringent and people are higher and higher to the cry for improving environmental quality, and alkaline residue processing is increasingly taken seriously.
At present, it is common to use alkaline residue processing method be mainly neutralisation, biochemical method and wet oxidation process etc., wherein neutralizing
Method generally uses the acidic materials such as the concentrated sulfuric acid, sulfur dioxide to carry out acidification to alkaline residue as acidizing reagent, reduces alkaline residue alkali
Degree removes most sulfide in alkaline sewage, and recycles petroleum acids, and the method technique is relatively simple, and plant investment is low, gives up
Water treatment efficiency is obvious, therefore neutralizing alkaline residue processing is a universal treatment process.However, in actual alkaline residue acidification mistake
Cheng Zhong, since, containing a large amount of easy foaming substance, and acid-base reaction releases a large amount of heat facilitates the generation of foam in alkaline residue,
The presence of a large amount of foams is unfavorable for radiating, and hinders the progress of acid-base reaction, and will cause and block liquid flooding tower phenomenon, so that discharge
Tail gas in contain a large amount of alkaline residue, influence the stable operation of device.
CN201210176565.6 disclose a kind of caustic sludge desulfuration dephenolize neutralization and tail gas desulfurization processing combined method and
Device, wherein device includes that alkaline residue oxidation sweetening tower, alkaline residue filter, carbonization settling tank, fiber film contactor and tail gas are inhaled
Attached digester, alkaline residue oxidation sweetening top of tower are connect by tail gas discharging pipe one with tail gas adsorption digester, alkaline residue oxidation sweetening
Tower bottom is connect by alkaline residue delivery pipe with alkaline residue filter, and alkaline residue filter is contacted by alkaline residue feed pipe two with fiber liquid film
Device connection, fiber film contactor bottom are fixed on carbonization settling tank by flange；Method the following steps are included: by alkaline residue according to
Secondary progress oxidation processes, air lift essence take off disulphide processing, remove mechanical admixture and colloid, separation hydrogen sulfide and mercaptan, absorption
Desulfurization process.This method alkaline residue first has to by desulfurization process, can generate desulfidation tail gas, and needs by finish adsorption treatment
After could discharge, the sulfur-bearing finish after absorption tail gas goes finished pot to reconcile.Alkaline residue after desulfurization process need to be added 1-5 times it is fresh
Water or demineralized water dilution, can just be neutralized.
CN200920199634.9 and US5997731 discloses the alkaline residue treatment process of a kind of sulfur-bearing and phenol, using fibre
Tie up membrane contactor combination carbon dioxide neutralize and gasoline extract dephenolize technology, its advantage is that by the carbonization treatments such as phenol sodium generate phenol with
Vulcanized sodium carbonization treatment is generated hydrogen sulfide and sodium carbonate by sodium bisulfate, by the small organic molecules separate out such as mercaptan thioether,
The hydrogen sulfide of generation, phenol and mercaptan thioether can be extracted back in light-end products, solve generation hydrogen sulfide, phenol in carbonisation
And the processing problem of mercaptan thioether.But being acidified in the technique using carbon dioxide necessarily causes alkaline residue acidification to be not thorough,
To keep the removal rate of the pollutants such as alkaline residue COD poor, and, carbon dioxide and oil not high using the device integrated level of this technique
The blended absorbent efficiency of product is poor, so that the inefficient increase with installation area of acidification, it is even more important that due to acid
A large amount of neutralization reaction heat is generated during changing, and substantially reduces extraction efficiency.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of refinery basic sewage acidification reaction device and acidifications
Method.The present invention can reduce the heat that acidification reaction generates while alkaline residue is acidified, and greatly increase what acidification generated
The absorption efficiency of hydrogen sulfide, mercaptan thioether；And acidification reaction device is with structure is simple, degree of integration is high, occupied area is small, inhales
Receive and be acidified the features such as high-efficient.
Refinery basic sewage acidification reaction device of the present invention, including oil-gas mixer, air-fuel mixture tower, air-fuel mixture pump, acidification
Reaction tower and acidizing pump, wherein oil-gas mixer import respectively with SO2Gas feed pipe is connected with finish feed pipe, outlet and oil
Gas mixing column import connects, and successively sets fiber-film contact, collecting tank, diversion pipe, diversion pipe from top to bottom in air-fuel mixture tower
Bottom end is deep under tower reactor liquid level；Air-fuel mixture pump inlet is connect with air-fuel mixture tower tower reactor, and outlet is connect with finish feed pipe；
The acidification reaction tower is telescoping structure, and inner cylinder is extraction tower, and outer cylinder is connected to acidification reaction tower tower reactor；Be acidified pump inlet with
The connection of acidification reaction tower tower reactor, outlet are connect with extraction tower lower part；Air-fuel mixture tower tower reactor and acidification reaction tower tower reactor are by overflowing
Flow tube connection, the mixed liquor of air-fuel mixture tower tower reactor are overflowed in acidification reaction tower tower reactor by this overflow pipe.
The oil-gas mixer is pumped using air-fuel mixture or pipe-line mixer, and SO may be implemented2Gas and finish it is pre-
Mixing.Oil-gas mixer preferably uses multiphase flow pump, and SO not only may be implemented2Gas and finish are sufficiently mixed, and can be with
Finish is improved to SO2Absorbability, help to improve acidizing effect.
The air-fuel mixture tower and acidification reaction tower use conventional use of cylindricality tower, ratio of height to diameter 8-20, preferably 10-
18；Tower reactor diameter and upper end tower body diameter ratio are 1-5, and preferably tower reactor diameter is greater than upper end tower body diameter.The collecting tank is preferred
It is set in air-fuel mixture tower tower reactor, it is 10-40mm diversion pipe that collecting tank lower end, which is uniformly arranged multiple diameters, and diversion pipe bottom end is deep
Enter under tower reactor liquid level.The diversion pipe being arranged in principle is The more the better, can make mixed effect more preferably.
The acidification reaction tower outer barrel diameter is 1.1-2 times of inner cylinder extraction tower diameter, outer cylinder upper end opening, with big gas phase
Logical, lower end is connected to tower reactor.The upper end of the inner cylinder extraction tower seals, and the cylindricality tower of bottom diameter is greater than using upper-end inner diameter,
It is preferred that tapered reaction tower is arranged using upper end, the conical surface of upper end taper tower wall is provided with downwards multiple extractant overflow ports, overflows
The quantity of head piece is The more the better in principle.The extraction tower does not limit specific form, can for spray column, perforated-plate extraction tower,
The extraction tower form of the transmissions such as packed extraction tower and turntable extracting tower.
Another object of the present invention, which also resides in, provides a kind of acidization tool using above-mentioned refinery basic sewage acidification reaction device,
Including following content:
(1) finish and SO2Gas is passed through in oil-gas mixer and is pre-mixed, and then passes to the fiber in air-fuel mixture tower
Double absorption is carried out in membrane contactor, finally enters in collecting tank and progress depth suction under tower reactor liquid level is entered by diversion pipe
It receives, and blended absorbent repeatedly is carried out by air-fuel mixture pump；
(2) SO is absorbed2Finish afterwards overflows to acidification reaction tower tower reactor by overflow pipe from air-fuel mixture tower tower reactor
In, and extraction tower is sent to by acidizing pump and is reacted with refinery basic sewage progress adverse current acidizing extraction；
(3) extraction reaction rich absorbent oil agent and acidification generate bubble pass through be arranged in extraction tower upper end several overflow
Head piece is flowed down along acidification reaction tower outer tube inner wall from above, while the gas not absorbed by finish is by logical between inner barrel and outer barrel
Road is discharged to outside tower；
(4) alkaline residue is discharged to outside system in extraction tower lower part after being acidified, while rich absorbent oil agent is discharged to system by acidizing pump
Outside.
In the present invention, SO is can be directly used in step (1)2Purified gases can also use and contain SO2Gas, such as use
S-Zorb adsorbent reactivation flue gas is passed through a certain amount of inert gas such as nitrogen and is blended, and controls SO2Volumetric concentration is 5%-
80%.The finish is that hydrogen kerosene raffinate to be added, diesel oil, naphtha etc. prepare finish into hydrogenation device for treatment, the finish with
SO2Volume ratio with inert gas gaseous mixture is 0.005-0.5, preferably 0.02-0.1；The operating pressure for controlling mixed process is small
In 10kPa.SO of the present invention2It is pre-mixed in oil-gas mixer first with inert gas gaseous mixture with finish, then
It is passed through in the fiber-film contact in air-fuel mixture tower and carries out secondary blended absorbent, finally enter the liquid collecting of air-fuel mixture tower lower end
Tower reactor finish liquid level or less is entered by diversion pipe in slot and carries out depth blended absorbent, is operated by above-mentioned blended absorbent, pole
Finish is increased to SO greatly2Absorption efficiency.
In the present invention, step (2) absorbs SO2Neutralization reaction occurs for finish and alkali residue waste liquid afterwards, with acidification reaction
It carries out, most of organic sulfur compound, H in alkali residue waste liquid2S, phenol etc. is entered in finish with molecular conformation.During acidification,
It controls operating pressure and is less than 10kPa；The ratio of alkaline residue and finish be 1:1-1:30, preferably 1:3-1:10, with guarantee sulfide and
Petroleum acids completely removes, and finally obtains the acidifying solution that pH is 2-5.After acidified processing, the COD removal rate of alkali residue waste liquid can
Up to 90% or more, organic sulfur compound and H2S removal rate is up to 99% or more, and volatile phenol removal rate is up to 95% or more.
In the present invention, big calorimetric is released in step (3) described acidization, temperature raising is unfavorable for finish to acidization
Organic sulfur compound, the H of generation2S, the absorption of the pollutants such as phenol, therefore the present invention is discharged heat using following methods, is reduced and is inhaled
Receive finish temperature: rich absorbent oil agent extracted is by being arranged under several overflow port overflows of extraction tower upper end, preferably
Rich absorbent oil agent is flow down along acidification reaction tower outer tube inner wall wall in overflow port setting diversion pipe, due to inert gas, such as N2
Solubility in finish is far smaller than SO2, therefore the channel that inert gas passes through from the bottom to top between inner barrel and outer barrel is discharged to acid
To change outside reaction tower, inert gas is inversely contacted with the higher finish of temperature to get off from upper end overflow, make the reduction of finish temperature, from
And increase the absorption efficiency of finish.The inert gas of discharge can enter incinerator, or part returns to oil-gas mixer again
Carry out air-fuel mixture.
In the present invention, the rich absorbent oil agent after step (4) partial extraction absorbs is discharged at hydro-refining unit
Reason.
Compared with prior art, the present invention has a characteristic that
(1) present invention does not need pre-desulfurization, and acidization does not generate acidification tail gas, without secondary pollution, acidification dress
Set that structure is simple, degree of integration is high, occupied area is small.
(2) SO2Oil-gas mixer premixing, fiber-film contact second level blended absorbent and collecting tank are successively carried out with finish
With the depth blended absorbent of diversion pipe, finish is considerably increased to SO2Absorption efficiency.
And CO (3))2It is compared as acidizing reagent, using SO2With inert gas gaseous mixture as acidizing reagent, alkali is deepened
Slag is acidified depth, makes souring operation condition that can reach higher pollutants removal rate under normal pressure, greatly reduces device
Construction cost and operation difficulty.And due to inert gas and SO2Different solubility in finish discharges in acidization
The high temperature finish generated in inert gas and acidization inversely contacts, and high degree reduces finish temperature, to improve
Absorption finish is to organic sulfur compound, H2S, the absorption efficiency of the pollutants such as phenol.
(4) since overflow port is arranged in present apparatus acidification reaction tower upper end, make to generate a large amount of gas in refinery basic sewage acidization
Bubble overflows back tower reactor, thus phenomena such as effectively preventing liquid foam entrainment.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of acidification reaction device of the present invention；
Description of symbols in figure: 1-SO2With inert gas gaseous mixture, 2- finish, 3- oil-gas mixer, 4- air-fuel mixture pump,
5- air-fuel mixture tower, 6- fiber-film contact, 7- collecting tank, 8- collecting tank diversion pipe, 9- air-fuel mixture tower tower reactor, 10- overflow
Pipe, 11- acidification reaction tower tower reactor, 12- acidification reaction tower, 13- extraction tower, 14- extraction tower packing, 15- extraction tower overflow port,
16- inert gas, 17- refinery basic sewage, 18- acidizing pump, alkaline residue after 19- acidification, 20- rich absorbent oil agent, outside 21- acidification reaction tower
Cylinder.
Specific embodiment
Refinery basic sewage acidification reaction device of the present invention is as shown in Fig. 1, including oil-gas mixer 3, air-fuel mixture tower 5, oil
Gas mixing pump 4, acidification reaction tower 12 and acidizing pump 18.3 import of oil-gas mixer respectively with SO2With inert gas gaseous mixture 1 into
Expects pipe is connected with 2 feed pipe of finish, and oil-gas mixer outlet is connect with 5 import of air-fuel mixture tower.In air-fuel mixture tower on toward
Under successively set fiber-film contact 6, collecting tank 7, diversion pipe 8,8 bottom end of diversion pipe is deep into the liquid level of air-fuel mixture tower tower reactor 9
Under.Air-fuel mixture pumps 4 imports and connect with air-fuel mixture tower tower reactor 9, and outlet is connect with 2 feed pipe of finish；The acidification reaction tower
12 be telescoping structure, and inner cylinder is extraction tower 13, and outer cylinder 21 is connected to acidification reaction tower tower reactor 11；18 import of acidizing pump and acidification
Reaction tower tower reactor 11 connects, and outlet is connect with extraction tower lower part；Air-fuel mixture tower tower reactor and acidification reaction tower tower reactor pass through overflow
Pipe 10 is connected to, and the mixed liquor of air-fuel mixture tower tower reactor is overflowed in acidification reaction tower tower reactor by this overflow pipe.
The oil-gas mixer uses pipe-line mixer or multiphase flow pump.The air-fuel mixture tower and acidification reaction tower use
Conventional use of cylindricality tower, ratio of height to diameter 8-20, preferably 10-18；Tower reactor diameter and upper end tower body diameter ratio are 1-5, preferably
Greater than upper end tower body diameter.The collecting tank is located in air-fuel mixture tower tower reactor, and collecting tank lower end is uniformly arranged multiple diameters and is
10-40mm diversion pipe, diversion pipe bottom end need to be deep under tower reactor liquid level.The diversion pipe being arranged in principle is The more the better.
The acidification reaction tower outer barrel diameter is 1.1-2 times of inner cylinder extraction tower diameter, outer cylinder upper end opening, with big gas phase
Logical, lower end is connected to tower reactor.The upper end of the inner cylinder extraction tower seals, and tapered reaction tower, upper end cone are arranged using upper end
The conical surface of shape tower wall is provided with downwards multiple extractant overflow ports 15, and the quantity of overflow port is The more the better in principle.The extraction tower
Equipped with filler 14.
When above-mentioned acidification reaction device works, SO first2It is mixed that it is passed through oil gas simultaneously with inert gas gaseous mixture 1 and finish 2
It is tentatively mixed in clutch 3, carries out secondary blended absorbent subsequently into the fiber-film contact 6 in air-fuel mixture tower 5, finally
Enter under tower reactor liquid level progress depth blended absorbent into diversion pipe 8 is passed through in collecting tank 7, and by air-fuel mixture pump 4 into
Capable blended absorbent repeatedly.Absorb SO2Finish afterwards overflows to acidification reaction by overflow pipe 10 from air-fuel mixture tower tower reactor 9
In tower tower reactor 11, and extraction 14 lower end of tower packing is sent to by acidizing pump 18 and extracts the oil refining alkali of tower packing upper end charging
Slag 17 carries out the reaction of adverse current acidizing extraction.The bubble generated in the rich absorbent oil agent 20 and acidization that extraction reaction generates passes through
Several overflow ports 15 of extraction tower upper end are set, is flowed down along 21 inner wall of acidification reaction tower tower body outer cylinder from above, is not had simultaneously
It is discharged to outside acidification reaction tower 12 by the channel between inner barrel and outer barrel from the bottom to top by the inert gas 16 that finish absorbs；After acidification
Alkaline residue 19 is discharged to outside system in 13 lower part of extraction tower, while rich absorbent oil agent 20 is also discharged to outside system by acidizing pump 18.
Technical solutions and effects of the present invention is described in detail below with reference to embodiment.
Embodiment 1
Certain plant catalytic gasoline alkaline residue, wherein COD is 3.21 × 105Mg/L, sulfide are 1.76 × 104mg/L.Using attached
The acidification reaction device of Fig. 1 carries out acidification to it, and oil-gas mixer uses pipe-line mixer, and air-fuel mixture tower and acidification are anti-
The ratio of height to diameter for answering tower is 10, and air-fuel mixture tower tower reactor and acidification reaction tower tower reactor diameter and upper end tower body diameter ratio are 2.Oil gas is mixed
The collecting tank closed in tower tower reactor is opened type cube structure, is set in tower reactor, collecting tank lower end is uniformly arranged 30 diameters
For the diversion pipe of 15mm.Acidification reaction tower outer barrel diameter is 1.2 times of inner cylinder extraction tower diameter, and upper end opening is communicated with atmosphere,
Lower end is connected to acidification reaction tower tower reactor.Extraction tower is packed tower, and upper end setting is tapered, and the conical surface of taper tower wall is provided with downwards
8 extractant overflow ports.It using S-Zorb adsorbent reactivation flue gas is come from, is passed through nitrogen and is blended, control SO2Volumetric concentration
It is 5%, the finish used is to hydrofining diesel oil, finish and SO2Volume ratio with the gaseous mixture of inert gas is 0.05；It is mixed
The operating pressure of conjunction process is less than 10kPa.When alkaline residue is acidified, the ratio of alkaline residue and finish is 1:4, and finally obtaining pH is 5 or so
Acidifying solution.After acidified processing, the COD removal rate of alkali residue waste liquid is 90%, organic sulfur compound and H2S removal rate up to 99%,
Volatile phenol removal rate is up to 95%.
Embodiment 2
Certain plant catalytic gasoline alkaline residue, wherein COD is 7.97 × 104Mg/L, sulfide are 4 × 103mg/L.Using attached drawing 1
Acidification reaction device carry out acidification to it, oil-gas mixer uses pipe-line mixer, air-fuel mixture tower and acidification reaction
The ratio of height to diameter of tower is 18, and air-fuel mixture tower tower reactor and acidification reaction tower tower reactor diameter and upper end tower body diameter ratio are 5.Air-fuel mixture
Collecting tank in tower tower reactor is hemisphere, and cambered surface downward, is set in tower reactor, and collecting tank lower end is uniformly arranged 20 diameters and is
The diversion pipe of 40mm.Acidification reaction tower outer barrel diameter is 2 times of inner cylinder extraction tower diameter, and upper end opening is communicated with atmosphere, lower end
It is connected to acidification reaction tower tower reactor.Extraction tower is packed tower, and upper end setting is tapered, and the conical surface of taper tower wall is provided with downwards 4
Extractant overflow port.Using pure SO2Gas is passed through nitrogen and is blended, and controls SO2Volumetric concentration is 10%, the finish used for
To hydrofinishing naphtha, finish and SO2Volume ratio with the gaseous mixture of inert gas is 0.5；The operating pressure of mixed process
Less than 10kPa.When alkaline residue is acidified, the ratio of alkaline residue and finish is 1:10, finally obtains the acidifying solution that pH is 4 or so.Through peracid
After change processing, the COD removal rate of alkali residue waste liquid is 94%, organic sulfur compound and H2Up to 99%, volatile phenol removal rate reaches S removal rate
96%。
Embodiment 3
Treatment process and operating condition with embodiment 1, the difference is that: using multiphase flow pump replace pipe-line mixer,
Due to improving finish to SO2Absorbability, finally obtain pH be 4 or so acidifying solution.After acidified processing, alkaline residue is useless
The COD removal rate of liquid is 93%, organic sulfur compound and H2S removal rate is up to 99%, and volatile phenol removal rate is up to 97%.
Embodiment 4
Treatment process and operating condition with embodiment 2, the difference is that: using multiphase flow pump replace pipe-line mixer,
Due to improving finish to SO2Absorbability, finally obtain pH be 3 or so acidifying solution.After acidified processing, alkaline residue is useless
The COD removal rate of liquid is 95%, organic sulfur compound and H2S removal rate is up to 99%, and volatile phenol removal rate is up to 98%.
Comparative example 1
Treatment process and operating condition with embodiment 1, the difference is that: be not provided with collecting tank in air-fuel mixture tower tower reactor
And diversion pipe, finally obtain the acidifying solution that pH is 6 or so.After acidified processing, the COD removal rate of alkali residue waste liquid is 86%, is had
Machine sulfide and H2S removal rate is 98%, and volatile phenol removal rate is 93%, removal effect decline.
Comparative example 2
Treatment process and operating condition with embodiment 1, the difference is that: acidification reaction do not use inner/outer drum structure and overflow
Flow tube, using common spray column.After acidified processing, the COD removal rate of alkali residue waste liquid is 71%, organic sulfur compound and H2S
Removal rate is 98%, and volatile phenol removal rate is 65%.
Comparative example 3
Treatment process and operating condition with embodiment 1, the difference is that: be not passed through inert gas, but be passed through air
It is blended.Due to introducing oxygen in system, so that containing a large amount of sulfate radical after acidification in alkaline residue, it is not suitable for using causticization
Regeneration technology processing；And there are flammability hazards when mixing with gasoline for gas, reduce the applicability of device.
Claims (15)
1. a kind of refinery basic sewage acidification reaction device, it is characterised in that including oil-gas mixer, air-fuel mixture tower, air-fuel mixture
Pump, acidification reaction tower and acidizing pump, wherein oil-gas mixer import respectively with SO2Gas feed pipe is connected with finish feed pipe,
Outlet is connect with air-fuel mixture tower import, successively sets fiber-film contact, collecting tank, water conservancy diversion in air-fuel mixture tower from top to bottom
Pipe, diversion pipe bottom end is deep under tower reactor liquid level；Air-fuel mixture pump inlet is connect with air-fuel mixture tower tower reactor, outlet and finish into
Expects pipe connection；The acidification reaction tower is telescoping structure, and inner cylinder is extraction tower, and outer cylinder is connected to acidification reaction tower tower reactor；Acid
Change pump inlet to connect with acidification reaction tower tower reactor, outlet is connect with extraction tower lower part；Air-fuel mixture tower tower reactor and acidification reaction tower
Tower reactor is connected to by overflow pipe, and the mixed liquor of air-fuel mixture tower tower reactor is overflowed in acidification reaction tower tower reactor by this overflow pipe.
2. the apparatus according to claim 1, it is characterised in that: the oil-gas mixer uses multiphase flow pump.
3. the apparatus according to claim 1, it is characterised in that: the air-fuel mixture tower and acidification reaction tower use cylindricality
Tower, ratio of height to diameter 8-20, tower reactor diameter and upper end tower body diameter ratio are 1-5.
4. the apparatus according to claim 1, it is characterised in that: the collecting tank is set in air-fuel mixture tower tower reactor, collection
It is 10-40mm diversion pipe that liquid bath lower end, which is uniformly arranged multiple diameters, and diversion pipe bottom end is deep under tower reactor liquid level.
5. the apparatus according to claim 1, it is characterised in that: the acidification reaction tower outer barrel diameter is that inner cylinder extraction tower is straight
1.1-2 times of diameter, outer cylinder upper end opening, communicates with atmosphere, and lower end is connected to tower reactor.
6. the apparatus according to claim 1, it is characterised in that: the inner cylinder extraction tower is spray column, perforated-plate extraction tower, fills out
Expect extraction tower or turntable extracting tower, upper end sealing is arranged tapered reaction tower using upper end, the conical surface of upper end taper tower wall to
Under be provided with multiple extractant overflow ports.
7. using the refinery basic sewage acidization tool of any described device of claim 1-6, it is characterised in that including following content:
(1) finish and SO2Gas is passed through in oil-gas mixer and is pre-mixed, and the tunica fibrosa then passed in air-fuel mixture tower connects
Double absorption is carried out in tentaculum, finally enters in collecting tank and progress depth absorption under tower reactor liquid level is entered by diversion pipe, and
Blended absorbent repeatedly is carried out by air-fuel mixture pump；
(2) SO is absorbed2Finish afterwards is overflowed in acidification reaction tower tower reactor by overflow pipe from air-fuel mixture tower tower reactor, and led to
Peracid pump is sent to extraction tower and reacts with refinery basic sewage progress adverse current acidizing extraction；
(3) the rich absorbent oil agent of extraction reaction and the bubble of acidification generation pass through several overflows that extraction tower upper end is arranged in
Mouthful, it is flowed down along acidification reaction tower outer tube inner wall from above, while the gas not absorbed by finish is by the channel between inner barrel and outer barrel
It is discharged to outside tower；
(4) alkaline residue is discharged to outside system in extraction tower lower part after being acidified, while rich absorbent oil agent is discharged to outside system by acidizing pump.
8. according to the method described in claim 7, it is characterized by: step (1) uses pure SO2Gas contains SO2Gas
Body is passed through a certain amount of inert gas and is blended, and controls SO2Volumetric concentration is 5%-80%.
9. according to the method described in claim 8, it is characterized by: step (1) is passed through using S-Zorb adsorbent reactivation flue gas
Nitrogen is blended.
10. according to the method described in claim 7, it is characterized by: the finish is hydrogen kerosene raffinate to be added, diesel oil or stone brain
Oil, the finish and SO2Volume ratio with inert gas gaseous mixture is 0.005-0.5, and the operating pressure for controlling mixed process is small
In 10kPa.
11. according to the method described in claim 10, it is characterized by: the finish and SO2With the volume of inert gas gaseous mixture
Than for 0.02-0.1.
12. according to the method described in claim 7, it is characterized by: controlling operating pressure during step (2) acidification
Less than 10kPa；The ratio of alkaline residue and finish is that 1:1-1:30 is finally obtained with guaranteeing completely removing for sulfide and petroleum acids
PH is the acidifying solution of 2-5.
13. according to the method for claim 12, it is characterised in that: during step (2) acidification, alkaline residue and finish
Ratio is 1:3-1:10.
14. according to the method described in claim 7, it is characterized by: step (3) rich absorbent oil agent extracted is existed by setting
Several overflow port overflows of extraction tower upper end are got off, overflow port setting diversion pipe by rich absorbent oil agent outside acidification reaction tower
Cylinder inner wall flows down.
15. according to the method described in claim 7, it is characterized by: the rich absorbent oil agent after step (4) extraction absorbs is arranged
Enter hydro-refining unit to be handled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510800824.1A CN106745442B (en) | 2015-11-19 | 2015-11-19 | A kind of refinery basic sewage acidification reaction device and acidization tool |
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| CN201510800824.1A CN106745442B (en) | 2015-11-19 | 2015-11-19 | A kind of refinery basic sewage acidification reaction device and acidization tool |
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| CN109095583B (en) * | 2018-09-25 | 2021-10-29 | 东营联合石化有限责任公司 | Comprehensive treatment device for oil refining alkaline residue waste liquid |
| CN109095584B (en) * | 2018-09-25 | 2021-10-29 | 东营联合石化有限责任公司 | Oil refining alkaline residue waste liquid treatment process |
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| CN201579249U (en) * | 2009-11-05 | 2010-09-15 | 宁波中一石化科技有限公司 | Device for treating alkaline residue generated by desulfurizing light oil |
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