CN108067089B - A kind of method and apparatus producing NaHS - Google Patents
A kind of method and apparatus producing NaHS Download PDFInfo
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- CN108067089B CN108067089B CN201610990978.6A CN201610990978A CN108067089B CN 108067089 B CN108067089 B CN 108067089B CN 201610990978 A CN201610990978 A CN 201610990978A CN 108067089 B CN108067089 B CN 108067089B
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/32—Hydrosulfides of sodium or potassium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
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- B01D2251/304—Alkali metal compounds of sodium
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Abstract
The invention discloses a kind of method and apparatus for producing NaHS, including following content: by by the H in sour gas2S, which is absorbed to be transferred in low temperature diesel oil, obtains rich absorbent oil, carries out acid-base neutralization reaction using NaOH solution and rich absorbent oil, removes H2S, through water-oil separating, water phase is mutually recycled with oil.The present invention absorbs acid-base neutralization reaction heat using low temperature diesel oil, acid-base neutralization reaction is exactly the regenerative process of absorbent, there is no concern that causing moisture transition evaporation to generate the local-crystalized of salt since local acid-base neutralization reaction heat is excessive, and block pipeline or reactor.NaHS solution product produced by the invention meets the requirement of " industrial NaHS " GB23937-2009 liquid L-1 kind product.
Description
Technical field
The invention belongs to environmental protection and chemical technology fields, more particularly to a kind of method and apparatus for producing NaHS.
Background technique
It in hydrofinishing, is hydrocracked, in the crude oil secondary processing process such as catalytic cracking, the testing sulphide in crude oil is when big
It is partially converted into hydrogen sulfide, and is present in sour gas.When as fuel or raw material, pipeline and equipment can be caused
Corrosion, and hydrogen sulfide therein is also the raw material for manufacturing sulphur and sulfuric acid.Currently, alkanolamine solution is widely used to refinery in oil plant
Sour gas carries out depriving hydrogen sulphide processing, and the dry gas after depriving hydrogen sulphide is incorporated to gas pipe network, and hydrogen sulfide is then used to manufacture sulphur.By
In alkanolamine solution to H2S and CO2Selectivity it is limited, in sour gas after processing remove the H containing high concentration2Outside S, also
CO containing higher concentration2, general hydrogen sulfide content 85% or so, carbon dioxide content accounts for about 10%, and in addition there are also a small amount of hydro carbons
Gas, including methane and ethane etc..
Large and medium-sized sour gas is mainly for the production of sulphur, and there are two types of common technologies, another one is Claus technique
Kind is the LO-CAT technique of MERICHEM company, U.S. exploitation.Claus technique is using conventional low-temperature catalyzed turn of thermal response+second level
Micronizing technology produces sulphur, its advantage is that technical maturity, is suitble to produce the device of sulphur 5000t or more per year, sulfur recovery rate is most
High energy reaches 99% or more, but still has part sulphur with SO2Form be discharged into atmosphere, so needing to increase exhaust gas processing device.LO-
CAT technique makes H using the iron catalyst of multicomponent chelate2S is converted into elementary sulfur, H2The removal efficiency of S is more than 99.9%.LO-CAT
Technique can be suitble to acid tolerance to fluctuate various operating conditions of the larger and hydrogen sulfide content 0~100%, but due to operating cost
Valuableness, the sulfur purity and color of production, which are slightly worse than the drusen generated in claus process and production process, to be occurred
Clogging etc., in middle-size and small-size refinery, which is not so good as Claus technique.For small-sized refinery, because acid
Tolerance is little, and for many years, sour gas is discharging directly into atmosphere after burning mostly, wastes a large amount of Sulphur ressource, also results in relatively tight
The atmosphere pollution of weight.With the raising of national environmental standard, the Acidic Gas Treating of small-sized refinery increasingly draws attention.
To increase added value of product, many little refinery plants produce NaHS as raw material using sour gas, but due to acid
Hydrogen sulfide contained in property gas and carbon dioxide belong to sour gas, and property is similar, and the content of carbon dioxide spreads out to hydrogen sulfide
The quality and production cost of production product are affected, and since the crystallization of sodium carbonate etc. causes the blocking of pipeline and valve etc.,
Huge difficulty is brought to the normal production operation of device, NaHS product purity is also greatly affected.Therefore, guaranteeing
H in sour gas2Under the premise of S qualified discharge, the blocking of pipe valve and instrument etc. during solution NaHS production operation
It has very important significance with product purity etc. is improved for the utilization of sour gas.
CN103721531A is separated to carbon dioxide in sour gas and hydrogen sulfide using membrane technology and is absorbed life
Produce NaHS the disadvantages of there are low efficiencys.CN103754833A handles oil refinery dry gas with high-gravity technology, and produces more high-purity
The NaHS product of degree, product and by-product crystallization easily cause hypergravity machine operating unbalance, and acid-base neutralization reaction
Occur in revolving bed, reaction heat also generates immediately, needs to be added a large amount of carrier gas just and can guarantee reaction required temperature.
CN103861544A impinging streams mixer hits slot by reactor shell, reaction and liquid delivery pump is constituted, and reaction is hit in slot
Guide shell there are two being symmetrically installed.Fluid, which is hit in slot by guide shell in reaction, occurs impingement mix, rear to be hit by open
Slot enters in pyramidal structure liquid collection trough.Volume of fluid circulated is smaller in the technology reactive tank, and the impingement mix of two kinds of fluids is complete
Conveying equipment for fluid substances is depended on entirely, and operating cost is larger, also higher to the installation requirement of symmetrically arranged guide shell.
CN1814344A there is a problem of identical as CN103861544A.CN104656174B liquid liquid impinging streams mixer is in each water conservancy diversion
It is mounted on agitating paddle in cylinder, to guarantee that fluid can axially be flowed without bias current in guide shell along guide shell, needs to stir
It mixes paddle and guide shell is co-axially mounted, installation requirement is higher.CN205035335U makes two containing gas-liquid two-phase by atomizer
Fluid streams impingement mix with react, mixing depends on the touch opportunity and contact area of droplet with reaction efficiency, and efficiency is lower.
Summary of the invention
In view of the deficiencies of the prior art, the invention proposes a kind of method and apparatus for producing NaHS.Benefit of the invention
Reach the requirement of " industrial NaHS " GB23937-2009 liquid L-1 kind product with the NaHS liquid product that sour gas produces.
The method of production NaHS of the invention, including following content:
(1) diesel oil is entered after refrigeration system is freezed by absorption tower top, and the sour gas entered with absorb the bottom of the tower connects
It touches, the H in sour gas2S, which is absorbed to be transferred in low temperature diesel oil, obtains rich absorbent oil, removes H2Sour gas after S is removed through demister
After mist, gas pipe network is discharged by tower top, rich absorbent oil is discharged into level-one liquid liquid mixer；
(2) absorbing liquid (Na in level-one liquid liquid mixer, after rich absorbent oil and atomization2S solution) hybrid reaction, richness suction
Receive H in oil2S is converted into NaHS, and the liquid phase mixture after reaction enters level-one settling tank；Wherein absorbing liquid is heavy from level-one
The circulating absorption solution of tank and second level settling tank drops；
(3) in level-one settling tank, liquid phase mixture contains higher concentration H after water-oil separating2The oily phase of S, by level-one
Settling tank is discharged into second level liquid liquid mixer, and circulating absorption solution of the aqueous portion as level-one liquid liquid mixer is partially used as NaHS
Solution head product is sold after further oil removing as product；
(4) in second level liquid liquid mixer, the absorbing liquid haptoreaction of the oil phase and atomization come from level-one settling tank, instead
Liquid phase mixture after answering enters second level settling tank；Wherein absorbing liquid is fresh NaOH solution and the circulation from second level settling tank
Absorbing liquid；
(5) in second level settling tank, liquid phase mixture is after water-oil separating, and oil mutually returns to refrigeration system and is recycled, water
Mutually circulating absorption solution of the part as second level liquid liquid mixer, circulating absorption solution of the partial reflux as level-one liquid liquid mixer.
In the method for the present invention, H in the sour gas2S concentration of volume percent is 50%~95%, CO2Percent by volume is dense
Degree is 4%~20%, other for organic matters such as hydro carbons.
In the method for the present invention, the absorbing liquid is NaOH solution, and mass concentration is 10%~60%, preferably 20%~40%.
It is 9.5~12 by control second level settling tank aqueous pH values in the method for the present invention, adjusts fresh NaOH solution and be added
Amount.
In the method for the present invention, returns to the liquid measure of second level liquid liquid mixer and return to the ratio of the liquid measure of level-one liquid liquid mixer
For 2~8:1, preferably 3~5:1.
In the method for the present invention, the diesel fuel temperature after step (1) refrigeration is -30~10 DEG C, preferably -10~10 DEG C, purified
Gas phase afterwards is discharged into gas official website.
In the method for the present invention, multiple atomization sprays are provided with along axial direction in level-one liquid liquid mixer and second level liquid liquid mixer
Mouth, pressure of the absorbing liquid at nozzle are 0.1~0.3MPaG.
In the method for the present invention, continuous phase is oily phase in level-one liquid liquid mixer and second level liquid liquid mixer, and dispersed phase is equal
For absorbing liquid, oil is mutually 5~10:1 with the flow-rate ratio of absorbing liquid.Oily mutually 0.5~5m/s of flow velocity in pipeline, preferably 1.0
~3.0m/s.
In the method for the present invention, circulating absorption solution described in step (3) and head product flow-rate ratio are 2~8:1, preferably 3~5:
1。
In the method for the present invention, the level-one settling tank and second level settling tank are followed successively by gas-phase space, demisting from top to bottom
Device, water-oil separating area, oily phase buffer area and NaHS/Na2S solution buffer area, settling tank residence time are 0.5~3.0h, preferably
1.0~2.0h.
In the method for the present invention, in level-one settling tank and second level settling tank, by the gas phase that is precipitated in liquid phase through demister demisting
Afterwards, venturi-type eductors top entry is returned, is brought by unstripped gas into the negative pressure that venturi mixer trunnion generates is crossed.
Present invention simultaneously provides a kind of devices for producing NaHS, comprising: diesel oil refrigeration system, venturi mixer,
Diesel oil absorption tower, level-one liquid liquid mixer, level-one settling tank, second level liquid liquid mixer and second level settling tank；Venturi mixer
Side entrance is connect with sour gas feed line, and venturi mixer top entry is through gas at the top of pipeline and level-one settling tank
Mutually outlet and second level settling tank top gas phase outlet connection, venturi mixer are exported through pipeline and absorb the bottom of the tower gas phase entrance
Connection；Diesel raw material pipeline is connect through refrigeration system with absorption tower upper aqueous phase entrance；Absorb the bottom of the tower liquid-phase outlet is through pipeline
It is connect with level-one liquid liquid mixer oil phase entrance；Level-one liquid liquid mixer water phase entrance through pipeline respectively with level-one settling tank and two
The bottom cycle absorbing liquid discharge pipe connection of grade settling tank, level-one liquid liquid mixer liquid-phase outlet is through pipeline and level-one settling tank
Liquid phase entrance connection, level-one settling tank oil mutually outlet is connect through pipeline with second level liquid liquid mixer oil phase entrance, level-one sink
The water phase outlet of drop tank is divided into two-way, connects level-one liquid liquid mixer water phase entrance all the way, connects NaHS head product pipeline all the way；
The circulating absorption solution pipeline of fresh NaOH solution feed line and second level sedimentation pot bottom merge after with second level liquid liquid mixer
The connection of water phase entrance, second level liquid liquid mixer liquid-phase outlet are connect through pipeline with second level settling tank liquid phase entrance, level-one settling tank
Oil mutually outlet is connect through pipeline with refrigeration system entrance, the water phase of level-one settling tank, which exports, is divided into two-way, connects second level all the way
Liquid liquid mixer water phase entrance, another way connect level-one liquid liquid mixer water phase entrance.
In apparatus of the present invention, several sprays are disposed with along axial direction in level-one liquid liquid mixer and second level liquid liquid mixer
Mouth.
In apparatus of the present invention, in level-one settling tank, it is disposed with level-one settling tank gas-phase space, demisting from top to bottom
Device, level-one settling tank water-oil separating area, level-one settling tank oil phase buffer area and level-one settling tank NaHS solution buffer area；Logistics warp
Liquid phase entrance enters the water-oil separating area of settling tank in level-one settling tank after water-oil separating, and oil mutually enters oily phase buffer area,
Water phase enters NaHS solution buffer area.It is respectively arranged with tank level control system in two buffer areas, controls the discharge of liquid phase；
In apparatus of the present invention, in second level settling tank, it is disposed with second level settling tank gas-phase space, demisting from top to bottom
Device, second level settling tank water-oil separating area, second level settling tank oil phase buffer area and second level settling tank NaHS/Na2S solution buffer area；
Logistics enters the water-oil separating area of settling tank in level-one settling tank after water-oil separating through liquid phase entrance, and it is mutually slow that oil mutually enters oil
Area is rushed, water phase enters NaHS/Na2S solution buffer area.It is respectively arranged with tank level control system in two buffer areas, controls liquid
The discharge of phase, wherein the H in oily phase2S reacts completely, in second level settling tank NaHS/Na2S solution buffer area is additionally provided with pH inspection
Survey and control system make pH value be maintained at 9.5~12.0 by controlling NaOH solution additional amount.
Present invention simultaneously provides a kind of settling tank, two pieces of the liquid distribution above and below settling tank liquid phase inlet is horizontally disposed
Disk, the diameter d of distribution plate are 0.6~0.8 times of settling tank diameter D, have been provided on liquid distributing pan multiple round and/or rectangular
Hole, perforated area are the 30%~90%, preferably 50%~70% of distribution plate surface area, and the distance h between liquid distributing pan enters for liquid phase
1 ~ 3 times of mouth pipe diameter d ', liquid phase inlet duct continues to prolong forward in the space of the formation of upper and lower two pieces of liquid distributing pans
The length of 2/3~4/5 tank diameter is stretched, flow deflector is arranged in liquid phase inlet duct end.
It in the prior art,, can be to sedimentation due to the frictional force between liquid after liquid phase enters settling tank with certain flow rate
The liquid of the adjacent area of pot liquid flow direction causes to disturb, to make the more difficult separation of water-oil phase.The present invention is using upper
The settling tank stated can make liquid phase full of entire liquid distributing pan, first when liquid phase enters liquid distributing pan so as to avoid liquid
Body enters the disturbance after settling tank to flow direction adjacent area liquid, and liquid is big to the disturbance of adjacent area liquid phase in settling tank
Big to reduce, water-oil phase is able to flow downward with more uniform speed, so that water-oil separating be rapidly completed.
Compared with prior art, the present invention has the advantage that
(1) present invention can be by most H in sour gas with low temperature diesel processing sour gas2S absorbs washing and enters bavin
In oil, absorbed H2S content accounts for 95% or more into sour gas total content in diesel oil, to produce higher concentration
NaHS solution, at the same the process for producing NaHS be changed to by the acid-base neutralization reaction between gas-liquid in the prior art it is anti-between liquid phase
It answers, acid-base neutralization reaction heat can directly be absorbed by diesel oil, without the excessive steaming for worrying to lead to local moisture because of hot-spot
Hair is to generate the crystallization of salt and block pipeline or reactor.
(2) H is absorbed2The hybrid reaction process of diesel oil and NaOH solution after S is exactly the regenerative process of absorbent diesel oil, and
The Analytic Tower of rich absorbent oil need not be separately provided, simplify process.Na in present invention NaHS solution produced2S mass concentration
< 1.2% reaches the requirement of " industrial NaHS " GB23937-2009 liquid L-1 kind product.
(3) in liquid liquid mixer of the invention with oily mutually for continuous phase, absorbing liquid is dispersed phase, and setting is multiple in mixer
Atomizer for being atomized to absorbing liquid, and with the H in oily phase2S hybrid reaction, to form duct type percussion flow mixing
Device, be very suitable for the mixing of two kinds of fluids that flow difference is larger or reaction is faster with react so that in lye and diesel oil
H2S fast reaction.
(4) settling tank of the invention by using special construction, fluid flow-disturbing phenomenon of liquid phase in settling tank subtract significantly
Weak, so that water-oil phase quick separating, settling tank highly significant is reduced.
Detailed description of the invention
Fig. 1 is the method flow diagram of production NaHS of the invention.
Fig. 2 is liquid distributing pan structural schematic diagram in settling tank of the present invention.
Fig. 3 is flowing and water-oil separating schematic diagram of the fluid in settling tank when being not provided with liquid distributing pan.
Fig. 4 is after liquid enters settling tank of the present invention, and fluid flowing of (settling tank cross section) in liquid distributing pan is shown
It is intended to.
Fig. 5 is liquid after settling tank liquid distributing pan of the present invention, fluid in settling tank (axial direction) flow schematic diagram.
Wherein: 1, sour gas；2, diesel oil；3, refrigeration system；4, venturi mixer；5, diesel oil absorption tower；6, it removes
Day with fog；7, purified gas；8, rich absorbent oil pumps；9, level-one liquid liquid mixer；10, nozzle；11, primary cycle pumps；12, NaHS is produced
Product；13, level-one settling tank；14, first order reaction purified gas；15, demister；16, level-one settling tank oil phase liquid position Detection & Controling
System；17, level-one settling tank oil pump；18, NaOH solution；19, second level liquid liquid mixer；20, valve；21, secondary cycle pumps；
22, aqueous pH values measurement and control system；23, second level settling tank water phase level sensing and control system；24, second order reaction purifies
Gas；25, second level settling tank；26, second level settling tank oil phase liquid position measurement and control system；27, second level settling tank oil circulating pump；
28, level-one liquid liquid mixer exports liquid phase；29, second level liquid liquid mixer exports liquid phase；30, liquid distributing pan.
13-1, level-one settling tank gas-phase space；13-2, level-one settling tank water-oil separating area；13-3, level-one settling tank oil phase
Buffer area；13-4, level-one settling tank NaHS solution buffer area.
25-1, second level settling tank gas-phase space；25-2, second level settling tank water-oil separating area；25-3, second level settling tank oil phase
Buffer area；25-4, second level settling tank NaHS/Na2S solution buffer area.
Specific embodiment
The method of the present invention and device are described in more detail below by specific embodiment, but and are not so limited this
Invention.
The method of production NaHS of the invention, be carried out as follows: sour gas (1) is mixed through venturi
When device (4), the purified gas of negative-pressure ward level-one settling tank (13) and second level settling tank (25) is generated, and by absorption tower (5) bottom
Portion enters, and diesel oil (2) enters absorption tower by absorption tower (5) top after refrigeration system (3) cool down；The two is in absorption tower (5)
Counter current contacting, the H in sour gas2S is absorbed by low temperature diesel oil to be transferred in liquid phase diesel oil by gas phase.Purified gas (7) is discharged into gas
Pipe network, liquid phase are discharged into level-one liquid liquid mixer (9) by rich absorbent oil pump (8), pump spraying through atomization for (11) with through primary cycle
Absorbing liquid counter current contacting reaction after mouth (10) atomization, H during being somebody's turn to do2S is excessive, the H in diesel oil2S is converted into NaHS.Level-one
Liquid liquid mixer outlet liquid phase (28) enters level-one settling tank (13) and carries out water-oil separating afterwards, the gas phase (14) being precipitated from liquid phase
Venturi mixer (4) entrance is returned to by top.Liquid phase is lye and diesel oil, and immiscible, the two is after sedimentation separation, oily phase
It is controlled by level sensing and control system (16) and is pumped into second level liquid liquid mixer (19) through level-one settling tank oil pump (17).Water phase by
Level sensing and control system (31), which are controlled, is divided into two-way through primary cycle pump (11), and wherein liquid phase (12) is that NaHS solution goes out
Product, another way (32) pump the absorption after the circulating absorption solution (21-2) come mixes as level-one liquid liquid mixer with secondary cycle
Liquid.In second level liquid liquid mixer, what the oily Xiang Yujing second level absorbing liquid circulating pump (21) that level-one settling tank comes was come sprays through atomization
The H in oily phase is removed in depth in circulating absorption solution hybrid reaction after mouth (10) atomization2S during this, is inhaled by control loop
Liquid pH is received 9.5~12, adjusts the additional amount of fresh NaOH solution (20), NaOH is excessive during being somebody's turn to do, and reaction primary product is
Na2S.Second level liquid liquid mixer exports liquid phase (29) and enters second level settling tank (25), is returned by the gas phase that liquid phase is precipitated through tower top
Venturi mixer (4) entrance.Water-oil phase after sedimentation separation, mutually examined by second level settling tank oil circulating pump (27) through liquid level by oil
It surveys and returns to refrigeration system (3) recycling with control system (26) control.Water phase is alkaline absorption solution, through level sensing and control
System (23) control is divided into two-way after secondary cycle pumps (23), and (21-1) returns to second level liquid liquid mixer (19) all the way, another
As level-one liquid liquid mixer (9) absorbing liquid after absorbing liquid mixes after road (21-2) is pumped with primary cycle.(21-1) and (21-2)
Flow-rate ratio is 2~8:1, preferably 3~5:1.
In absorption tower (5), by low temperature diesel oil to the H in sour gas2S's is highly selective, by H2S is transferred to by gas phase
Liquid phase, to obtain rich absorbent oil.Due to containing the H of high concentration in rich absorbent oil2S, moreover, comparing circulating absorption solution (21-2)
(32) the alkaline matter in mixed liquor, H2S be it is excessive, reacted as follows in level-one liquid liquid mixer: Na2S + H2S
→ 2NaHS, in second level liquid liquid mixer, NaOH is excessive, is reacted as follows: H2S + 2NaOH → Na2S + 2H2O。
In the present invention, the production process of NaHS is also the resolving of diesel oil.Acid-base neutralization reaction heat can be by low temperature diesel oil
It is absorbed, eliminates recirculating cooling water system, structure of reactor is simplified.30~50 DEG C of diesel fuel temperature after regeneration returns
Refrigeration system is recycled.
Embodiment 1
Certain sour gas pressure 0.30MPaG, 30 DEG C of temperature, H in sour gas2S accounts for 55v%, CO2Concentration 10v%, hydro carbons
35v%。
Operating condition: (1) diesel oil density 849.7kg/m3, boiling range see the table below 1.Diesel fuel temperature -10 after refrigeration system
℃；(2) NaOH solution concentration 20% used in；(3) hydraulic detention time is 1.0h in settling tank；(4) it is absorbed in second level settling tank
Liquid (25-4) pH value 10；(5) circulation liquid phase (21-1) and the liquid phase (21-2) for returning to level-one liquid liquid mixer in second level settling tank
Ratio 3:1；(6) circulation liquid phase (32) and head product (12) ratio 3:1 in level-one settling tank.
As a result: the mass concentration 42.2% of NaHS, Na in NaHS solution2S mass concentration 0.8%, reaches GB23937-2009
The requirement of " industrial NaHS " NaHS liquid L-1 kind product.
1 diesel oil boiling range range of table.
| Temperature, DEG C | 177 | 223 | 280 | 341 | 361 |
| Boiling range, V% | 0 | 10 | 50 | 90 | 100 |
Embodiment 2
Certain sour gas pressure 0.30MPaG, 30 DEG C of temperature, H in sour gas2S accounts for 85v%, CO2Concentration 10v%, hydro carbons
5v%。
Operating condition: (1) diesel oil regulation used is same as Example 1 in absorption tower；Enter the bavin on absorption tower after condensing
- 5 DEG C of oil temperature；(2) NaOH solution concentration 25% used in；(3) settling tank hydraulic detention time is 1.5h；(4) second level settling tank
Interior circulating absorption solution pH value 9.5；(5) circulation liquid phase (21-1) and the liquid phase for returning to level-one liquid liquid mixer in second level settling tank
(21-2) ratio 4:1；(6) circulation liquid phase (32) and head product (12) ratio 4:1 in level-one settling tank；
As a result: the mass concentration 42.5% of NaHS, Na in NaHS solution2S mass concentration 0.6%, reaches GB23937-2009
The requirement of " industrial NaHS " NaHS liquid L-1 kind product.
Embodiment 3
Certain sour gas pressure 0.30MPaG, 30 DEG C of temperature, H in sour gas2S accounts for 93v%, CO2Concentration 5v%, hydro carbons
2v%。
Operating condition: (1) diesel oil regulation used is same as Example 1 in absorption tower；Enter the bavin on absorption tower after condensing
0 DEG C of oil temperature；(2) NaOH solution concentration 30% used in；(3) settling tank hydraulic detention time is 2.0h；(4) second level settling tank
Interior circulating absorption solution pH value 10.5；(5) circulation liquid phase (21-1) and the liquid phase for returning to level-one liquid liquid mixer in second level settling tank
(21-2) ratio 5:1；(6) circulation liquid phase (32) and head product (12) ratio 5:1 in level-one settling tank.
As a result: the mass concentration 43.0% of NaHS, Na in NaHS solution product2S mass concentration 0.2%, reaches GB23937-
The requirement of 2009 " industrial NaHS " NaHS liquid L-1 kind product.
Claims (13)
1. a kind of method for producing NaHS, including following content: (1) diesel oil is after refrigeration system is freezed, by absorption tower
Portion enters, and the sour gas entered with absorb the bottom of the tower contacts, the H in sour gas2S, which is absorbed to be transferred in low temperature diesel oil, obtains richness
Oil is absorbed, H is removed2Sour gas after S is discharged into gas pipe network after demister demisting, by tower top, and rich absorbent oil is discharged into level-one liquid
Liquid mixer；(2) in level-one liquid liquid mixer, absorbing liquid hybrid reaction after rich absorbent oil and atomization, H in rich absorbent oil2S
It is converted into NaHS, the liquid phase mixture after reaction enters level-one settling tank；Wherein absorbing liquid is from level-one settling tank and two
The circulating absorption solution of grade settling tank；(3) in level-one settling tank, liquid phase mixture contains higher concentration H after water-oil separating2S
Oily phase, second level liquid liquid mixer is discharged by level-one settling tank, circulating absorption solution of the aqueous portion as level-one liquid liquid mixer,
Part is used as NaHS solution head product, after further oil removing, sells as product；(4) it in second level liquid liquid mixer, comes from
For the oil of level-one settling tank mutually with the absorbing liquid haptoreaction of atomization, the liquid phase mixture after reaction enters second level settling tank；Wherein
Absorbing liquid is fresh NaOH solution and the circulating absorption solution from second level settling tank；(5) in second level settling tank, liquid phase mixture
After water-oil separating, oil mutually returns to refrigeration system and is recycled, circulating absorption solution of the aqueous portion as second level liquid liquid mixer,
Circulating absorption solution of the partial reflux as level-one liquid liquid mixer.
2. according to the method for claim 1, it is characterised in that: H in the sour gas2S concentration of volume percent is 50%
~95%, CO2Concentration of volume percent is 4 %~20%.
3. according to the method for claim 1, it is characterised in that: by control second level settling tank aqueous pH values be 9.5~12,
Adjust fresh NaOH solution additional amount.
4. according to the method for claim 1, it is characterised in that: return to the liquid measure of second level liquid liquid mixer and return to level-one liquid
The ratio of the liquid measure of liquid mixer is 2~8:1.
5. according to the method for claim 1, it is characterised in that: the diesel fuel temperature after step (1) refrigeration is -30~10 DEG C.
6. according to the method for claim 1, it is characterised in that: along axis in level-one liquid liquid mixer and second level liquid liquid mixer
To multiple atomizers are provided with, pressure of the absorbing liquid at nozzle is 0.1~0.3MPaG.
7. according to the method for claim 1, it is characterised in that: continuous in level-one liquid liquid mixer and second level liquid liquid mixer
It is mutually oily phase, dispersed phase is absorbing liquid, and oil is mutually 5~10:1 with the flow-rate ratio of absorbing liquid.
8. according to the method for claim 1, it is characterised in that: circulating absorption solution described in step (3) and head product flow
Than for 2~8:1.
9. according to the method for claim 1, it is characterised in that: when the stop of level-one settling tank and the second level settling tank
Between be 0.5~3.0h.
10. a kind of device for producing NaHS, characterized by comprising: diesel oil refrigeration system, venturi mixer, diesel oil are inhaled
Receive tower, level-one liquid liquid mixer, level-one settling tank, second level liquid liquid mixer and second level settling tank；Venturi mixer laterally enters
Mouth is connect with sour gas feed line, and venturi mixer top entry is exported through pipeline and level-one settling tank top gas phase
It exports and connects with second level settling tank top gas phase, venturi mixer outlet is connect through pipeline with absorb the bottom of the tower gas phase entrance；
Diesel raw material pipeline is connect through refrigeration system with absorption tower upper aqueous phase entrance；Absorb the bottom of the tower liquid-phase outlet is through pipeline and level-one
The connection of liquid liquid mixer oil phase entrance；Level-one liquid liquid mixer water phase entrance is settled with level-one settling tank and second level respectively through pipeline
The bottom cycle absorbing liquid discharge pipe of tank connects, liquid phase of the level-one liquid liquid mixer liquid-phase outlet through pipeline Yu level-one settling tank
Entrance connection, mutually outlet is connect through pipeline with second level liquid liquid mixer oil phase entrance the oil of level-one settling tank, level-one settling tank
Water phase outlet is divided into two-way, connects level-one liquid liquid mixer water phase entrance all the way, connects NaHS head product pipeline all the way；Fresh
NaOH solution feed line enters after merging with the circulating absorption solution pipeline of second level sedimentation pot bottom with second level liquid liquid mixer water phase
Mouth connection, second level liquid liquid mixer liquid-phase outlet are connect through pipeline with second level settling tank liquid phase entrance, the oily phase of level-one settling tank
Outlet is connect through pipeline with refrigeration system entrance, and the water phase outlet of level-one settling tank is divided into two-way, and it is mixed to connect second level liquid liquid all the way
Clutch water phase entrance, another way connect level-one liquid liquid mixer water phase entrance.
11. device according to claim 10, it is characterised in that: in level-one liquid liquid mixer and second level liquid liquid mixer
Several nozzles are disposed with along axial direction.
12. device according to claim 10, it is characterised in that: in level-one settling tank, be disposed with from top to bottom
Level-one settling tank gas-phase space, demister, level-one settling tank water-oil separating area, level-one settling tank oil phase buffer area and level-one sedimentation
Tank NaHS solution buffer area；Logistics enters the water-oil separating area of settling tank in level-one settling tank through water-oil separating through liquid phase entrance
Afterwards, oil mutually enters oily phase buffer area, and water phase enters NaHS solution buffer area；Liquid level is respectively arranged in two buffer areas
System controls the discharge of liquid phase.
13. device according to claim 10, it is characterised in that: in second level settling tank, be disposed with from top to bottom
Second level settling tank gas-phase space, demister, second level settling tank water-oil separating area, second level settling tank oil phase buffer area and second level sedimentation
Tank NaHS/Na2S solution buffer area；Logistics enters the water-oil separating area of settling tank in level-one settling tank through oil through liquid phase entrance
After water separation, oil mutually enters oily phase buffer area, and water phase enters NaHS/Na2S solution buffer area；It is set respectively in two buffer areas
It is equipped with tank level control system, controls the discharge of liquid phase；In second level settling tank NaHS/Na2S solution buffer area is additionally provided with pH detection
With control system.
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| CN104449814B (en) * | 2013-09-12 | 2016-05-11 | 中国石化工程建设有限公司 | A kind of hydrogenation system and method for hydrotreating of producing ultra-low-sulphur diesel |
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| CN104826463B (en) * | 2014-02-10 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of sour gas produces NaHS technique and device |
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