CN109420417A - A kind of hydration method separation sour gas technique and device - Google Patents
A kind of hydration method separation sour gas technique and device Download PDFInfo
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- CN109420417A CN109420417A CN201710715572.1A CN201710715572A CN109420417A CN 109420417 A CN109420417 A CN 109420417A CN 201710715572 A CN201710715572 A CN 201710715572A CN 109420417 A CN109420417 A CN 109420417A
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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
- B01D53/75—Multi-step processes
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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
- B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
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- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- B01D—SEPARATION
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- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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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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- B01D2251/604—Hydroxides
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Abstract
It include hydration reactor, decomposition of hydrate device, absorbing reaction device and products pot the invention discloses a kind of hydration method separation sour gas technique and device, described device；The connection of the gas phase entrance of sour gas feeding line and hydration reactor, the liquid-phase outlet of hydration reactor is connect with the hydrate slurry entrance of decomposition of hydrate device, and the cold purified liquor outlet of decomposition of hydrate device and the outlet of regeneration hydrate working solution are connect after cooler with the liquid phase entrance of hydrate reactor；Decomposition of hydrate device gaseous phase outlet is connect with the gas phase entrance of absorbing reaction device, and the gaseous phase outlet of absorbing reaction device is connect with clean gas outlet pipeline, and the liquid phase entrance of absorbing reaction device is connect with alkali liquor inlet pipeline.The present invention makes full use of the energy in whole technological process, and the exothermic heat of reaction Proper Match that the heat absorption of decomposition of hydrate and alkaline process are absorbed greatly reduces energy consumption.
Description
Technical field
The present invention relates to a kind of processing method and processing devices of sour gas, more particularly to a kind of carbonated and hydrogen sulfide
Acid gas purifying and pollutant resources recovery and utilization technology.
Background technique
Sour gas is a kind of processing tail gas generated in petroleum refining process, main component H2S and CO2.Refining
Factory's sour gas mostlys come from the devices such as sewage stripping, desulphurization of recycle hydrogen and dry gas and desulfuration of liquefied gas.Large-scale refinery's acid
Property tolerance it is larger (produce per year sulphur > 5000t/a), the Acidic Gas Treating device of production sulphur is generally all established, to H2S is returned
It receives and utilizes.And for medium and small refinery (producing sulphur < 5000t/a per year), since acidity is narrow-minded, sulphur unit higher cost is established,
Most of small refinery is substantially all handled sour gas by the way of burning and exhausting, and this method not only causes the waste of resource,
And the SO that burning generates2Huge pressure is brought to environmental protection.
Sour gas is administered according to the difference that product is made is recycled at present, can be divided into and be produced sulphur, Sulphuric acid and system Asia
Sulfate, NaHS etc. change product.
Producing sulfur product, there are mainly two types of mature technologies, and one is second level Claus+ tail gas hydrogenation reduction+solvent absorptions
Technology；Another kind is the LO-CAT technology of gas technology Products Co., Ltd, Merichem company, U.S. exploitation.Second level
Claus+ tail gas hydrogenation reduction+solvent absorption technical matters is mature, and product sulphur quality is stablized, but due to long flow path, investment it is big,
Energy consumption is high, equipment safety control requires height, and Claus technique can only handle the sour gas of high concentration, for small refinery's acid
Property gas improvement have no advantage.LO-CAT technique makes H using the iron catalyst of multicomponent chelate2S is converted into elementary sulfur, Neng Goushi
It closes acid tolerance and fluctuates biggish operating condition, H2The removal efficiency of S is high, but since there are operating cost height, sulfur purity by LO-CAT
The drusen for being slightly worse than claus process with color, and generating in process of production understands blockage phenomenon, in addition catalyst
The problems such as higher with patent royalties, so that the technology more difficult popularization in the improvement of small sour gas.
Sour gas relieving haperacidity technology can directly utilize sour gas relieving haperacidity, which saves, is at low cost, adaptable,
Production process is easy to operate.But sulfuric acid production process is more complex, takes up a large area, and transport, the storage of sulfuric acid acquire a certain degree of difficulty,
As its limiting factor.Sour gas production sulfite process process is simple, different absorbents can be used realizes product multiplicity
Change, but in its production process there are equipment seriously corroded, maintenance cost is higher and product marketing is unsmooth the problems such as, have certain
Limitation.
The comprehensive utilization of sour gas, can be using less novel absorbent method sulfur removal technology technology be invested, and production chemical industry produces
Product akali sulphide (Na2S/NaHS).Akali sulphide can be widely applied to the works such as ore dressing, pesticide, dyestuff, tanning production and organic synthesis
Industry.In addition to containing H in sour gas2Outside S gas, also contain a certain amount of CO2Gas, during producing akali sulphide,
CO2Gas can produce Na with raw material lye2CO3/NaHCO3Impurity causes process pipe in production process to block, production is caused to fill
Set can not long period continuous operation, and there are alkaline consumptions it is high, product purity is poor the problems such as.CN103551018A discloses one kind and contains
Sulphur tail gas clean-up and recoverying and utilizing method, using barium sulphide to CO in gas2It is removed, obtained H2S gas can produce height
The NaHS product of quality, but generate barium sulfite and barium carbonate sediment, it is difficult to it handles.A step disclosed in patent CN1109020A
The method that method prepares NaHS, using the liquid containing stereoplasm of lime and sodium sulphate to containing CO2H2S gas is handled, and has calcium carbonate etc.
Precipitating generates.In preparation NaHS method described in patent CN101186280A and CN101337661A, Solid state fermentation is equally faced
The problem of.Patent CN103754833A discloses a kind of device and method using oil refinery dry gas production NaHS, utilizes hypergravity
Technology carries out selective desulfurization processing to dry gas, obtains 99% H2The NaHS purity of S gas generation is up to 42% or more, but the skill
Art feed gas preprocessing long flow path, process units is complicated, and rich regeneration of absorption solution energy consumption is higher.CN103446849A,
NaHS production technology described in CN103466559A and CN103638802A equally faces process complexity, amine in sour gas pretreatment
The problems such as liquid regeneration energy consumption is higher.
In conclusion need to comprehensively consider the factors such as safe and environment-friendly, economy for the improvement of small-sized sour gas,
This just needs a kind of process short, and small investment is easy to operate, and energy consumption and operating cost are low and have the Synthetic of certain economic benefit
Reason mode.
Hydrate separation technology is the hot spot of recent domestic research, the technology simple, mild condition, behaviour by process
Make flexibly, green non-pollution the advantages that largely paid close attention to.The principle that Hydrate Technology separates gaseous mixture is that gas with various is formed
The differing pressure of hydrate is very big, and the pressure gap of hydrate is formed using gas with various, by controlling formation condition, Ji Keshi
The separation of existing mixing gas component.H in sour gas2S gas and CO2Gas and phase balance condition when water formation hydrate are poor
It is different larger, therefore can use the technology and sour gas is separated.But heat release and suction of the hydrate in generation and decomposition
Thermal energy consumption problem is the principal element for restricting the technical application.In addition, the liquid phase of conventional aqueous object method separation gas is using water-soluble
Liquid, the hydrate of generation are to be generally crystal habit, and the hydrate mobility of formation is poor, are easy aggregation blocking, directly restrict
Continuity, the scale application of hydrate the relevant technologies.It is to solve the flowability problem of hydrate in spite of the relevant technologies, adopts
It is conveyed with being granulated with hydrate slurry form, but granulating technique, needs to carry out dehydration procedure, recycle pelletizer to dehydration
Hydrate afterwards is processed, and process is complicated；And hydrate slurry form, it is that hydrate and unreacted are generated into the molten of hydrate
Circulation conveying solves flowability problem to liquid together, but causes to need integrally to heat up to mixed serum when decomposition of hydrate, decomposes
Whole cooling is carried out again after release gas, and energy consumption has been significantly greatly increased, has improved operating cost.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydration method separation sour gas technique and device, can be to acid
While property gas is handled, Na is produced2S or NaHS chemical products, by environmental improvement and Chemical Manufacture combination be
Integrated process.Compared with prior art, the method for the present invention can compared under temperate condition, economical and efficient to containing CO2Gas and
H2The sour gas of S gas is pre-processed, and guarantees the good mobility of hydrate in hydration method separative unit, and control alkaline process absorbs
The Na of unit2CO3 / NaHCO3Content, it is ensured that device is continuous, long-period stable operation；To the energy in whole technological process into
It has gone and has made full use of, the exothermic heat of reaction Proper Match that the heat absorption of decomposition of hydrate and alkaline process are absorbed greatly reduces energy consumption；It is whole
A treatment process environmental protection, reliable, nothing " three wastes " generate.
The present invention provides a kind of acid device of air of hydration method separation, and described device includes hydration reactor, decomposition of hydrate
Device, absorbing reaction device and products pot；The connection of the gas phase entrance of sour gas feeding line and hydration reactor, the liquid of hydration reactor
Mutually outlet is connect with the hydrate slurry entrance of the slurries separative unit of decomposition of hydrate device, and the lonely liquid of decomposition of hydrate device goes out
Mouth and the outlet of regeneration hydrate working solution are connect after cooler with the liquid phase entrance of hydrate reactor；Decomposition of hydrate device top
The gaseous phase outlet in portion is connect with the gas phase entrance of absorbing reaction device, and the gaseous phase outlet and clean gas outlet pipeline of absorbing reaction device connect
It connects, the liquid-phase outlet of absorbing reaction device divides two-way, and the first via is connect with products pot, and the second tunnel is through the heat exchange in decomposition of hydrate device
Equipment is connect with absorbing reaction device circulation fluid entrance, and the liquid phase entrance of absorbing reaction device is connect with alkali liquor inlet pipeline；Wherein institute
Stating decomposition of hydrate device includes slurries separative unit and decomposition unit, and the slurries separative unit and decomposition unit are logical by connection
Road connection；The slurries separative unit is divided into two parts up and down through filter screen separator component, and top is disposed with water from top to bottom
Object injection point, filter washing water inlet, interface channel interface are closed, lower part is lonely liquid reservoir, and liquid storage trench bottom is equipped with lonely liquid
Outlet；The decomposition unit is disposed with the outlet of decomposition of hydrate gas, interface channel interface and regenerated liquid liquid storage from top to bottom
Slot is provided with heat exchange unit, stripping gas entrance, the outlet of regeneration hydrate working solution in regenerated liquid reservoir.
In above-mentioned acidity device of air, compressor is set on sour gas feeding line, for guaranteeing acid atmospheric pressure and hydration
Reactor operating pressure matches.
In above-mentioned acidity device of air, the hydration reactor for the benefit of gas-liquid mass transfer and being set with good heat transfer effect
Standby, form is unlimited, can be one in stirring-type, atomizing, bubble type, sieve-board type, material filling type, hypergravity or shock flow type etc.
Kind, preferably using liquid phase as the consersion unit of continuous phase.Hydration reactor requires to may be configured as level-one or more according to mixed gas separation
Grade.
It is above-mentioned acidity device of air in, the absorbing reaction device be gas-liquid mass transfer consersion unit, specially bubbling column reactor,
One of filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor, preferably rotating bed reaction
Device.Absorbing reaction device requires to may be configured as one or more levels according to reaction product.
In above-mentioned acidity device of air, the interface channel in decomposition of hydrate device is horizontally disposed or inclines at an angle
Tiltedly setting makes slurries separative unit interface channel interface be higher than decomposition unit interface channel interface, inclination angle when being obliquely installed
Degree and horizontal plane are at 10 °~60 °, preferably 15 °~45 °.The lower plane of interface channel is placed in slurries separative unit vertical height
At 1/2~3/4.
In above-mentioned acidity device of air, the filter screen separator component in decomposition of hydrate device can be horizontally disposed with either in certain
Angle tilt setting, the upper plane of filter screen separator component and the lower plane of interface channel are arranged in same plane.The strainer every
Board group part is filtered processing to hydrate slurry using any one of filling-material structure, screen net structure or mesh structure, realization,
Filtered rich hydrate phase slurries (or grain crystalline shape) are delivered to decomposition unit, filtrate (lonely liquid) enters the storage of lower section
Liquid bath.The parameters such as aperture, porosity, the filling thickness of filter screen separator component need for gaseous mixture system, additive types and
It forms which kind of structure hydrate and is determined.
In above-mentioned acidity device of air, hydrate slurry entrance is connected with spray assemblies, the spray in decomposition of hydrate device
Liquid distribution trough well known in the art can be used in component, can be realized and hydrate slurry is sprayed and is uniformly distributed, and guarantees covering
Domain is entire slurries separative unit section.
In above-mentioned acidity device of air, the filter washing water inlet in decomposition of hydrate device is connected with nozzle, and the nozzle can be used
Arbitrary form well known in the art, can by cleaning solution high speed injection to filter screen separator component, area coverage account for entire strainer every
70% or more of board group part area realizes the washing souring to filter screen separator component, and nozzle is arranged in certain inclination angle, inclination
Direction towards interface channel, tilt angle and median vertical line at 5~45 °, preferably 10~30 °.
In above-mentioned acidity device of air, the lonely liquid reservoir liquid holdup in decomposition of hydrate device is the 1/3 of liquid storage sump volume
~2/3.
In above-mentioned acidity device of air, the regenerated liquid reservoir liquid holdup in decomposition of hydrate device is the 1/2 of liquid storage sump volume
~5/6.
In above-mentioned acidity device of air, wall-type heat exchange equipment, hot-fluid are provided in the heat exchange unit in decomposition of hydrate device
Body is walked tube side and is heated by coil form to hydrate slurry, and fin can be added outside coil pipe for enhanced heat exchange.
In above-mentioned acidity device of air, multiple groups are set between the coil pipe of heat exchange equipment in the decomposition unit in decomposition of hydrate device and are rolled over
Baffle is flowed, plays the role of supporting coil pipe and enhanced heat transfer effect.
In above-mentioned acidity device of air, decomposition of hydrate device is warm using the product liquid of absorbing reaction device output as heat exchange equipment
Source will be enriched in H2After the hydrate working solution heating of S gas, absorbing reaction device is returned.
In above-mentioned acidity device of air, the stripping gas entrance in decomposition of hydrate device is connected with gas distributor, gas distribution
The section of device and decomposition unit is uniformly distributed in maximum, connects stripping gas in decomposition unit and rich hydrate slurry reverse flow
Gas distributor well known in the art can be used in touching, the gas distributor, and the stripping gas can be the regeneration of this unit decomposition
Gas circulation, or the arbitrary gas not reacted with following process process.
In above-mentioned acidity device of air, the regeneration hydrate working solution outlet point of the decomposition unit bottom in decomposition of hydrate device
Two-way, wherein being connect all the way through pipeline with the filter washing water inlet, the regeneration hydrate work that decomposed unit bottom is discharged
Make liquid to use as interior circulating cleaning fluid, the regeneration hydrate working solution volume flow used as interior circulating cleaning fluid accounts for
1/5~1, preferably the 1/3~1/2 of total regeneration hydrate working solution volume flow.
The present invention provides a kind of hydration method separation sour gas technique, and the technique includes following content:
(1) raw material sour gas enters hydration reactor, reacts with hydrate working solution, the H in sour gas2S gas and water
The reaction of object working solution is closed, mutually forms hydrate slurry, CO into hydrate2In gas phase enrichment, and hydration reactor is discharged；
(2) obtained in step (1) to be rich in H2The hydrate slurry of S gas enters decomposition of hydrate device, in decomposition of hydrate device
The processing of slurries separative unit after obtain lonely liquid and rich hydrate phase slurries, lonely liquid enters the lonely liquid reservoir of lower section；
(3) obtain the cleaned liquid effect of rich hydrate phase slurries in step (2) and enter decomposition unit, in regenerated liquid reservoir with
Product liquid from absorbing reaction device exchanges heat, and is passed through stripping gas counter current contacting with decomposition unit bottom, and decomposition releases
H2S gas, while decomposition of hydrate obtains reproduction operation liquid, regeneration hydrate working solution is mixed with lonely liquid and the processing that cools down
Afterwards, hydration reactor is returned to be recycled；
(4) H that step (3) obtains2S gas enters absorbing reaction device, is reacted with lye, treated exhaust emissions, obtains
To product liquid divide two-way, the first via enters decomposition of hydrate device as returning to absorbing reaction device after heat source heat exchange, the second road into
Enter products pot.
In present invention process, the pressure of step (1) described sour gas and the operating pressure of hydration reactor match, acid
Atmospheric pressure is 0.1Mpa~3.0Mpa, preferably 0.3Mpa~1.5Mpa, when sour gas insufficient pressure, can be carried out by compressor
Pressurization.
In present invention process, step (1) the hydrate working solution dosage and sour gas volume ratio (mark condition) be 5~
100L/m3, preferably 10~50L/m3。
In present invention process, step (1) described hydration reactor for the benefit of gas-liquid mass transfer and with good heat transfer effect
Equipment, form is unlimited, can be the one of stirring-type, atomizing, bubble type, sieve-board type, material filling type, hypergravity or shock flow type etc.
Kind, preferably using liquid phase as the consersion unit of continuous phase.Hydration reactor requires to may be configured as level-one or more according to mixed gas separation
Grade.
In present invention process, in hydration reactor, H is utilized2S and CO2Gas forms the difference that balances each other of hydrate, leads to
Control formation condition is crossed, realizes the separation of mixed gas.The operating condition of hydration reactor are as follows: pressure 0.1Mpa~3.0Mpa,
It is preferred that 0.3Mpa~1.5Mpa, 0~15 DEG C of temperature, preferably 3~10 DEG C.
In present invention process, in step (1) described hydration reactor, hydrate slurry, which refers to, has formed hydrate and unreacted
The mixed solution of hydrate working solution is generated, it is 30%~80% that reaction controlling hydrate, which accounts for the volume ratio in hydrate slurry, excellent
Select 50%~70%.
In present invention process, H in the tail gas of step (1) described hydration reactor2S volume fraction is controlled in 1%~20%, CO2
Volume fraction is higher than 80%, can be incorporated to the refinery gas desulphurization system centralized processing of sour gas upstream.
In present invention process, the operating condition of step (2) the decomposition of hydrate device are as follows: pressure 0.02Mpa~2.0Mpa,
It is preferred that 0.05Mpa~1.0Mpa, 0~10 DEG C of slurries separative unit temperature, 10~40 DEG C of decomposition unit temperature.
In present invention process, hydrate slurry is divided into lonely liquid and mutually starched with rich hydrate by step (2) slurries separative unit
Liquid, the hydrate volume content in lonely liquid are lower than 10%, and the hydrate volume content in rich hydrate phase slurries is higher than 80%.
In present invention process, step (3) described stripping gas can be any gas not reacted with following process process
Body, such as nitrogen, inert gas are also possible to the decomposition gas part circulation that decomposition unit obtains.
In the method for the present invention, step (3) the regeneration hydrate working solution and lonely liquid after cooling temperature control 0~
15 DEG C, preferably 3~10 DEG C return to hydration reactor and are recycled.
In present invention process, H in the gas that step (3) the decomposition of hydrate device releases2S volume fraction is higher than 95%,
CO2Volume fraction is lower than 5%.
In present invention process, the absorbing reaction device is gas-liquid mass transfer consersion unit, preferably using gas phase as the anti-of continuous phase
Answer equipment, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reaction
One of device, preferably rotary drill reactor.Absorbing reaction device requires to may be configured as one or more levels according to reaction product.
In present invention process, the absorbing reaction device operating condition are as follows: pressure 0.02Mpa~2.0Mpa, preferably 0.1Mpa
~1.0Mpa, 70~95 DEG C of temperature, preferably 80~90 DEG C.
In present invention process, the lye is NaOH solution, and mass concentration is 20%~60%, preferably 32%~48%,
The H that dosage is released according to step (4)2S content is adjusted.
In present invention process, step (4) the product liquid that absorbing reaction device reacts described out divides two-way, and the first via enters
Decomposition of hydrate device is used as heat source, and the second tunnel enters products pot, and the first via and the product flow quantity ratio on the second tunnel are
20/1~1/1, preferably 10/1~2/1.
In present invention process, the decomposition of hydrate device is using the decomposition of hydrate device having the following structure, the hydration
Object decomposer includes slurries separative unit and decomposition unit, and the slurries separative unit and decomposition unit are connected by interface channel
It is logical；The slurries separative unit is divided into two parts up and down through filter screen separator component, and top is disposed with hydrate from top to bottom
Injection point, filter washing water inlet, interface channel interface, lower part are lonely liquid reservoir, and liquid storage trench bottom is equipped with cold purified liquor outlet；
The decomposition unit is disposed with the outlet of decomposition of hydrate gas, interface channel interface and regenerated liquid reservoir from top to bottom, then
Heat exchange unit, stripping gas entrance, the outlet of regeneration hydrate working solution are provided in raw liquid reservoir.
In above-mentioned decomposition of hydrate device, the interface channel is horizontally disposed or is obliquely installed at an angle, when
When being obliquely installed, slurries separative unit interface channel interface is made to be higher than decomposition unit interface channel interface, tilt angle and level
Face is at 10 °~60 °, preferably 15 °~45 °.The lower plane of interface channel is placed in the 1/2~3/4 of slurries separative unit vertical height
Place.
In above-mentioned decomposition of hydrate device, the filter screen separator component can be horizontally disposed with either to tilt at an angle and set
It sets, the upper plane of filter screen separator component and the lower plane of interface channel are arranged in same plane.The filter screen separator component uses
Any one of filling-material structure, screen net structure or mesh structure, realization are filtered processing to hydrate slurry, will be filtered
Rich hydrate phase slurries (or grain crystalline shape) are delivered to decomposition unit, and filtrate (lonely liquid) enters the reservoir of lower section.Strainer
The parameters such as aperture, porosity, the filling thickness of baffle assembly need for gaseous mixture system, additive types and form which kind of knot
Structure hydrate and be determined.
In above-mentioned decomposition of hydrate device, the hydrate slurry entrance is connected with spray assemblies, and the spray assemblies can be adopted
With liquid distribution trough well known in the art, it can be realized and hydrate slurry is sprayed and is uniformly distributed, guarantee that covering domain is entire
Slurries separative unit section.
In above-mentioned decomposition of hydrate device, the filter washing water inlet is connected with nozzle, and the nozzle can be used known in this field
Arbitrary form, can by cleaning solution high speed injection to filter screen separator component, area coverage accounts for entire filter screen separator component area
70% or more, realize that, to the washing souring of filter screen separator component, nozzle is arranged in certain inclination angle, inclined direction is towards company
Road is connected, tilt angle and median vertical line are at 5~45 °, and preferably 10~30 °.
In above-mentioned decomposition of hydrate device, the lonely liquid reservoir liquid holdup is the 1/3~2/3 of liquid storage sump volume.
In above-mentioned decomposition of hydrate device, the regenerated liquid reservoir liquid holdup is the 1/2~5/6 of liquid storage sump volume.
In above-mentioned decomposition of hydrate device, wall-type heat exchange equipment is provided in the heat exchange unit, it is logical that hot fluid walks tube side
It crosses coil form to heat hydrate slurry, fin can be added outside coil pipe for enhanced heat exchange.
In above-mentioned decomposition of hydrate device, multiple groups hydraulic barrier is set between the coil pipe of heat exchange equipment in the decomposition unit, is risen
To the effect of support coil pipe and enhanced heat transfer effect.
In above-mentioned decomposition of hydrate device, the stripping gas entrance is connected with gas distributor, and gas distributor and decomposition are single
The section of member is uniformly distributed in maximum, contacts stripping gas with rich hydrate slurry reverse flow in decomposition unit, the gas point
Gas distributor well known in the art can be used in cloth device, and the stripping gas can recycle for the regeneration gas of this unit decomposition, can also
The arbitrary gas that with following process process reacts not is thought.
In above-mentioned decomposition of hydrate device, the regeneration hydrate working solution outlet of the decomposition unit bottom divides two-way, wherein
It is connect all the way through pipeline with the filter washing water inlet, the regeneration hydrate working solution that decomposed unit bottom is discharged is as in
Circulating cleaning fluid uses, and the regeneration hydrate working solution volume flow Zhan used as interior circulating cleaning fluid always regenerates hydration
The 1/5~1 of object working solution volume flow, preferably 1/3~1/2.
In present invention process, the hydrate working solution is the aqueous solution added with auxiliary agent, and the auxiliary agent includes auxiliary agent
A, the auxiliary agent A are lauryl sodium sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), linear alkyl sodium sulfonate (LAB-
SA), one or more of alkyl polyglycoside (APG), mass fraction preferably 0.005%~1.0%, more preferable mass fraction
0.01%~0.5 %.
In present invention process, auxiliary agent B can also be added in the hydrate working solution, the auxiliary agent B is kerosene, diesel oil
One or more of with silicone oil, the volume ratio of water is 1/5~2/1, preferably 1/ in the additive amount and hydrate working solution of auxiliary agent B
3~1/1.When adding auxiliary agent B in the hydrate working solution, emulsifier is preferably added, selected emulsifier can be hydrophilic
Property emulsifier, form Water-In-Oil (o/w) type lotion, be also possible to lipophilic emulsifier, form oil-in-water (w/o) type cream
Liquid, the additive amount of emulsifier are 0.5%~3% with the mole fraction of water in hydrate working solution.
It can also include auxiliary agent C in the hydrate working solution in present invention process, the auxiliary agent C is N- methyl pyrrole
One or more of pyrrolidone, propene carbonate, sulfolane, N- N-formyl morpholine N, polyethylene glycol, the quality point of the auxiliary agent C
Number is 2%~30%, preferably 5%~20 %.
In present invention process, the sour gas can be the sour gas in various sources, be preferably applied to H2S volume content is
60%~95%, CO2Content is 5%~40%, tolerance in 50~1000 Nm3The middle-size and small-size sour gas of/h.
In present invention process, the high concentration H that is obtained after being handled by separative unit2S gas, can according to product needs,
The series for controlling absorbing reaction device produces Na with raw material lye2S or NaHS chemical products.
Compared with prior art, hydration method separation sour gas technique of the present invention and device have the advantages that
(1) present invention process is by environmental improvement and being combined into one of Chemical Manufacture process.Using under different condition, H2S
Gas and CO2Gas and water have the characteristic of the larger difference that balances each other when forming hydrate, make H by controlling hydrating condition2S gas
Hydrate, which is preferentially produced, with hydrate working solution enters hydrate phase, CO2Gas do not generate or generate hydrate less and in gas phase
It is enriched with and is discharged, to realize to H in sour gas2S gas and CO2The separation of gas.Whole process operating condition is more mild,
Good separating effect, operating flexibility is big, and treated, and sour gas can be divided into high concentration CO2Gas (volume fraction > 80%) and highly concentrated
Spend H2S gas (volume fraction > 95%)；Rich in H2The hydrate of S gas molecule decomposes in decomposition of hydrate device and releases height
Purity H2S gas, alkaline process absorptive unit is with high-purity H2S gas be raw material, by with raw material alkaline reaction, produce Na2S or
NaHS chemical products.Entire treatment process environmental protection, reliable, no waste residue and brine waste etc. " three wastes " generation.
(2) in the present invention, the working solution that the hydrate working solution used compounds for various ingredients, and with hydrate slurry shape
Formula conveying, is interacted by the compounding between auxiliary agent A, B, C three, can not only reduce gas-liquid interface tension, increases gas
Solubility and diffusion coefficient in the liquid phase, and working solution is increased to H2The solution absorption ability of S, is greatly facilitated liquid phase
Middle gas forms the generation of hydrate, effectively improves hydrate generating rate, increases hydrate gas storage density, and guarantee
The mobility of hydrate phase improves H2S and CO2While the separating effect of gas, the continuous and stable operation of device ensure that.
(3) present invention process and device have carried out reasonably optimizing and sufficiently benefit to the energy of entire Acidic Gas Treating process
With.The surplus heat that alkali absorption method generates is sufficiently used for the decomposition of hydrate in decomposition of hydrate device, while utilizing heat exchange
Product liquid reflux afterwards, realizes the homogenizing and control of absorptive unit reaction temperature field, reasonable utilization maximum system energy, greatly
Reduce plant energy consumption.
(4) decomposition of hydrate device provided by the invention has slurries separative unit and decomposition unit, respectively to hydrate slurry
Liquid is filtered separation and deep decomposition.Hydrate slurry is divided into rich hydrate phase and lonely liquid phase by slurries separative unit: cold
Hemihydrate content in clear liquid phase is extremely low, it is not necessary to heat up, can maintain lower temperature reuse；Water in rich hydrate phase
It closes object occupancy volume and is higher than 80%, carry out heating and decomposition treatment in decomposition unit, while high efficient heat exchanging and stripping means having been cooperated to strengthen
Decomposition of hydrate, washing of the reproduction operation liquid extension for slurries separative unit filter screen separator component are washed away.Such mode
Decomposer can to the hydrate slurry with mobility carry out efficient-decomposition, decomposition of hydrate is high-efficient, have self-cleaning
Function, it is easy to maintain, and greatly reduce the energy consumption of working solution cooling reuse after hydrate slurry heating is decomposed and decomposed.
Detailed description of the invention
Fig. 1 is that hydration method of the present invention separates sour gas technique and schematic device.
Fig. 2 is that hydration method of the present invention separates decomposition of hydrate device structural schematic diagram in sour gas technique and device.
Specific embodiment
It elaborates below in conjunction with Detailed description of the invention and embodiment to the processing method and processing device of sour gas of the invention, but
It is not intended to limit the present invention.
As shown in Fig. 2, decomposition of hydrate device of the present invention includes slurries separative unit and decomposition unit, the slurries point
It is connected to decomposition unit by interface channel 12 from unit；The slurries separative unit is divided into upper and lower two through filter screen separator component 5
Part, top are disposed with hydrate slurry entrance 1, filter washing water inlet 3, interface channel interface 19 from top to bottom, and lower part is
Lonely liquid reservoir 6, liquid storage trench bottom are equipped with cold purified liquor outlet 13；The decomposition unit is disposed with hydrate from top to bottom
Decomposition gas exports 11, interface channel interface 20 and regenerated liquid reservoir 7, successively sets from top to bottom in the regenerated liquid reservoir 7
It is equipped with heat exchange unit 10, stripping gas entrance 8, regeneration hydrate working solution outlet 14.The wherein separative unit hydrate slurry
Liquid entrance 1 is connected with spray assemblies 2；The interior circulating cleaning fluid entrance 3 is connected with Washing spray nozzle 4；The deep decomposition unit
Stripping gas entrance 8 is connected with stripping gas distributor 9；Described 10 one end of heat exchange equipment is heating agent entrance 15, and the other end goes out for heating agent
Mouth 16；Multiple groups hydraulic barrier 17 is set between the coil pipe of heat exchange unit in the regenerated liquid reservoir 7.
The decomposition of hydrate device course of work is as follows: hydrate slurry passes through decomposition of hydrate device hydrate slurry entrance
1 introduces decomposer, is sprayed downwards by spray assemblies 2, spray and lower hydrate slurry passes through at 5 filtering of filter screen separator component
Hydrate slurry is divided into rich hydrate phase and lonely liquid phase by reason, and the Washing spray nozzle 4 of 5 top of filter screen separator component passes through continuous
The washing of filter screen separator component 5 is washed away in circulating cleaning fluid realization in spraying, and filtered lonely liquid falls to lonely liquid liquid storage
Slot 6, lonely liquid are followed in the cold purified liquor outlet 13 of liquid storage trench bottom and are badly recycled to hydrate reactor, and rich hydrate is by connecting
It connects road 12 and enters regenerated liquid reservoir 7, rich hydrate carries out exchanging heat with heat exchange equipment 10 in regenerated liquid reservoir 7 and successively
The channel formed by hydraulic barrier 17, rich hydrate are constantly thermally decomposed during the falling process and are discharged gas, while
7 bottom of regenerated liquid reservoir is passed through stripping gas by stripping gas entrance 8, stripping gas after stripping gas distributor 9 is uniformly distributed with
Hydrate slurry counter current contacting, what decomposition of hydrate released high concentration is absorbed gas from the bottom to top, eventually by hydrate
11 discharge of decomposition gas outlet, the regeneration hydrate working solution after decomposition pass through the regeneration hydrate work of 7 bottom of regenerated liquid reservoir
Make liquid outlet 14 discharge, partial regeneration hydrate working solution 18 as interior circulating cleaning solution enter slurries separative unit to strainer every
Board group part 5 is washed, and remaining reproduction operation liquid is delivered to hydrate reactor after cooling is handled.
As shown in Figure 1, the present invention provides a kind of acid device of air of hydration method separation, described device includes hydration reactor
24, decomposition of hydrate device 27, cooler 29, absorbing reaction device 33 and products pot 40；Sour gas feeding line 21 is through compressor 22
It is connect with 24 gas phase entrance of hydrate reactor；The liquid-phase outlet of hydration reactor 24 is through pipeline 26 and decomposition of hydrate device 27
The connection of hydrate slurry entrance, 24 gaseous phase outlet of hydration reactor are connected with exhaust pipe 25 is separated；The decomposition of hydrate device
27 lonely liquid outlet line 28 and reproduction operation liquid outlet line 31 is connect with 29 entrance of heat exchange equipment, and heat exchange equipment 29 goes out
Mouth is connect through pipeline 30 with the liquid phase entrance of hydration reactor 24；The gaseous phase outlet at the top of the decomposition of hydrate device 27 is through pipe
The connection of line 32 is connect with the gas phase entrance of absorbing reaction device 33, the stripping gas entrance and stripping tracheae of 27 bottom of decomposition of hydrate device
Line 34 connects；The gaseous phase outlet of absorbing reaction device 33 with purification gas pipeline 35 connect, absorbing reaction device 33 also with lye supply pipe
Line 36 connects, and the liquid-phase outlet pipeline 38 of absorbing reaction device 33 divides two-way, and the first via is connect through pipeline 37 with products pot 40, and second
Road is connect through pipeline 39 with the entrance of the heat exchange unit of decomposition of hydrate device 27, the outlet of the heat exchange unit of decomposition of hydrate device 27
It is connect through pipeline 41 with the product liquid reflux inlet of absorbing reaction device 33.
Hydration method separation sour gas process flow of the present invention is as follows: the sour gas from feeding line 21 increases through compressor 22
Enter hydration reactor 24 after pressure and easily generates the H of hydrate in hydration reactor 242S gas enter hydrate phase (Gu
Liquid phase) slurries are formed, it is not easy to generate the CO of hydrate2Gas is discharged in gas phase enrichment, and by exhaust pipe 25, realizes acid
CO in property gas2Separation.H will be rich in hydration reactor 242The hydrate slurry of S gas introduces decomposition of hydrate through pipeline 26
The slurries separative unit of device 27, hydrate slurry enter through hydrate slurry entrance 1, are sprayed downwards by spray assemblies 2, spray
Hydrate slurry under and passes through 5 filtration treatment of filter screen separator component, and hydrate slurry is divided into rich hydrate phase and lonely liquid
The Washing spray nozzle 4 of phase, 5 top of filter screen separator component is realized by circulating cleaning fluid in constantly spraying to filter screen separator component 5
Washing is washed away, and filtered lonely liquid falls to lonely liquid reservoir 6, and rich hydrate is entering regenerated liquid by interface channel 12
Reservoir 7, rich hydrate are changed in regenerated liquid reservoir 7 by heat exchange equipment 10 and the high-temperature product liquid of absorptive unit
Heat, and the channel of the formation of hydraulic barrier 17 is passed sequentially through, rich hydrate is constantly thermally decomposed during the falling process and discharges gas
Body, while stripping gas is passed through by stripping gas entrance 8 in 7 bottom of regenerated liquid reservoir, stripping gas is uniform through stripping gas distributor 9
With hydrate slurry counter current contacting after distribution, decomposition of hydrate releases the H of high concentration2S gas from the bottom to top, eventually by water
11 discharge of object decomposition gas outlet is closed, the reproduction operation liquid after decomposition is exported by the reproduction operation liquid of 7 bottom of regenerated liquid reservoir
14 discharges, partial regeneration working solution 18 enter slurries separative unit as interior circulating cleaning solution and wash to filter screen separator component 5
It washs, remaining reproduction operation liquid enters heat exchange equipment 29 after cooling down together with lonely liquid, and it returns to hydration reactor 24 and is recycled,
The H released2S gas enters absorbing reaction device 33 by pipeline 32, is reacted with the lye from lye pipeline 36, reacts
The remaining lack of gas obtained after processing are discharged by clean gas outlet pipeline 35, and the product liquid reacted divides two-way, first via warp
Pipe 37 enters products pot 40 and stores, and the second tunnel enters decomposition of hydrate device 27 as heat source through pipeline 39 and heats to hydrate
Processing, the product liquid after heat exchange return to absorbing reaction device 33 through pipeline 41.
Embodiment 1
Certain sour gas amount Q=400Nm3/ h, pressure 0.7Mpa, wherein H2S volume fraction is 84%, CO2Volume fraction is
16%, remaining as substances such as hydro carbons.Sour gas is handled using processing method and processing device shown in Fig. 1.Wherein, hydrate
Decomposer is using decomposer structure described in Fig. 2.
Operating condition and treatment effect in treatment process is as follows: sour gas 21 draws after compressor 22 is pressurized to 1.2Mpa
Enter hydration reactor 24, reacts in hydration reactor 24 with hydrate working solution, reaction condition are as follows: pressure 1.2Mpa,
5 DEG C of temperature, hydrate working solution by water, the SDS that accounts for aqueous solution mass fraction 0.03%, the poly- second for accounting for aqueous solution mass fraction 10%
Sapn (fatty acid esters of sorbitan) emulsifier group that glycol, the diesel oil for being 1/4 with water volume ratio and water molar ratio are 0.8%
At reaction controlling hydrate production quantity accounts for 60% or so of hydrate slurry totality accumulated amount, in hydration reactor 24, H2S gas
Hydrate preferentially is generated with working solution and is enriched to hydrate phase, CO2And inert gas is arranged in gas phase enrichment and as tail gas
Out, the CO in tail gas2Concentration is 85% or so, is incorporated to the refinery gas desulphurization system centralized processing of sour gas upstream；It will hydration
Object slurries 26 are delivered to decomposition of hydrate device 27, and 27 condition of decomposition of hydrate device is pressure 0.5Mpa, and hydrate slurry 6 is in slurries
Separative unit is divided into the lonely liquid phase of the rich hydrate phase and 30% that account for slurries total amount 70%, wherein hydrate contains in lonely liquid
Amount about 10% or so enters lonely liquid reservoir, and the regenerated liquid that hemihydrate content is higher than that 80% enters decomposition unit in rich hydrate stores up
Liquid bath 7, regenerated liquid reservoir 7 maintain temperature at 22 DEG C or so by adjusting high-temperature product flow quantity, and rich hydrate slurry is added
High concentration H is released after heat2S gas, while reproduction operation liquid is obtained, reproduction operation liquid enters heat exchange equipment together with lonely liquid
29 after cooling down, and returns to hydration reactor 24 and is recycled, and 7 bottom of regenerated liquid reservoir employs nitrogen as stripping gas, hydration
CO in the gas discharged in object decomposer2Content < 3%；Obtained high concentration H2S gas enters absorbing reaction device 33 and 48%
NaOH solution reaction generates Na2S product, absorbing reaction device operating condition are as follows: pressure 0.4Mpa, 95 DEG C of temperature, absorbing reaction device
33 treated cleaning of off-gas discharges, obtained Na2S product liquid extension enters decomposition of hydrate device 7 and is heated, heat exchange
Absorbing reaction device 33 is returned to as interior circulation fluid afterwards, surplus products liquid enters the storage of products pot 40.By above-mentioned technique to refinery
Sour gas is handled the purified treatment for not only realizing sour gas, and has produced Na2S product, by sour gas change give up into
Treasured improves added value of product, converts environmental improvement to the production process of chemical products.Pair of this technical process economical and efficient
Containing CO2And H2The sour gas of S is pre-processed, and guarantees the good mobility of hydrate in hydration method separative unit, and control alkaline process is inhaled
Receive the Na of unit2CO3 / NaHCO3Content, it is ensured that device is continuous, long-period stable operation.In addition, passing through process optimization and this
Invention decomposition of hydrate device makes full use of the energy in whole technological process, greatly reduces energy consumption.
Comparative example 1
It is same as Example 1, the difference is that, decomposition of hydrate device reaches same treatment effect using conventional single column form
When fruit, 70% is decomposed into since hydrate slurry is first passed through separative unit by double tower stagewise decomposer used in Example 1
Rich hydrate phase and 30% lonely liquid phase, deep decomposition processing is mutually only then carried out to the rich hydrate for accounting for overall slurries 70%,
And using conventional decomposition tower in this comparative example, it needs the solution that hydrate and unreacted are generated to hydrate integrally to heat up, decomposes
The regenerated liquid obtained after release gas carries out whole cooling again, and energy consumption has been significantly greatly increased, has improved operating cost.With embodiment 1
It compares, working solution cooling overall energy consumption increases by 40% or more after the hydrate slurry heating of this comparative example is decomposed and decomposed.
Comparative example 2
It is same as Example 1, the difference is that being located in advance using traditional hydramine method " absorption-regeneration " technique to sour gas
Reason, absorbing liquid use the MDEA solution of mass fraction 30%, absorb 30 DEG C of temperature, 118 DEG C of regeneration temperature.Reach same treatment effect
When fruit, cause energy consumption larger since the regenerated temperature of amine liquid is higher, and the heat of decomposition of hydrate can be completely by alkali in embodiment 1
Method absorbs the reaction heat generated and provides, and compared with Example 1, the sour gas pretreatment energy consumption of this comparative example increases by 20% or more.
Claims (35)
1. a kind of hydration method separates acid device of air, described device includes hydration reactor, decomposition of hydrate device, absorbing reaction device
And products pot；The connection of the gas phase entrance of sour gas feeding line and hydration reactor, the liquid-phase outlet of hydration reactor and hydration
The hydrate slurry entrance of the slurries separative unit of object decomposer connects, the cold purified liquor outlet of decomposition of hydrate device and regeneration hydration
The outlet of object working solution is connect after cooler with the liquid phase entrance of hydrate reactor；Gaseous phase outlet at the top of decomposition of hydrate device
It is connect with the gas phase entrance of absorbing reaction device, the gaseous phase outlet of absorbing reaction device is connect with clean gas outlet pipeline, absorbing reaction
The liquid-phase outlet of device divides two-way, and the first via is connect with products pot, the second tunnel through in decomposition of hydrate device heat exchange equipment and absorption
The connection of reactor cycles liquid entrance, the liquid phase entrance of absorbing reaction device are connect with alkali liquor inlet pipeline；The wherein hydrate point
Solving device includes slurries separative unit and decomposition unit, and the slurries separative unit is connected to decomposition unit by interface channel；Institute
It states slurries separative unit and is divided into two parts up and down through filter screen separator component, top is disposed with hydrate slurry from top to bottom and enters
Mouth, filter washing water inlet, interface channel interface, lower part are lonely liquid reservoir, and liquid storage trench bottom is equipped with cold purified liquor outlet；Described point
Solution unit is disposed with the outlet of decomposition of hydrate gas, interface channel interface and regenerated liquid reservoir, regenerated liquid storage from top to bottom
Heat exchange unit, stripping gas entrance, the outlet of regeneration hydrate working solution are provided in liquid bath.
2. acidity device of air described in accordance with the claim 1, wherein compressor is arranged on sour gas feeding line, for guaranteeing
Acid atmospheric pressure matches with hydration reactor operating pressure.
3. acidity device of air described in accordance with the claim 1, wherein the absorbing reaction device is gas-liquid mass transfer consersion unit, tool
Body is one in bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor
Kind, preferably rotary drill reactor.
4. acidity device of air described in accordance with the claim 1, wherein interface channel in decomposition of hydrate device be it is horizontally disposed or
Person is to be obliquely installed at an angle, when being obliquely installed, connects slurries separative unit interface channel interface higher than decomposition unit
Pipeline joint is connected, tilt angle and horizontal plane are at 10 °~60 °, preferably 15 °~45 °.
5. acidity device of air described in accordance with the claim 1, wherein the lower plane of the interface channel in decomposition of hydrate device is placed in
At the 1/2~3/4 of slurries separative unit vertical height.
6. acidity device of air described in accordance with the claim 1, wherein the filter screen separator component level setting in decomposition of hydrate device
It is either obliquely installed at an angle, the upper plane of filter screen separator component and the lower plane of interface channel are in same plane cloth
It sets.
7. acidity device of air described in accordance with the claim 1, wherein the lonely liquid reservoir liquid holdup in decomposition of hydrate device is
The 1/3~2/3 of liquid storage sump volume.
8. acidity device of air described in accordance with the claim 1, wherein the regenerated liquid reservoir liquid holdup in decomposition of hydrate device is
The 1/2~5/6 of liquid storage sump volume.
9. acidity device of air described in accordance with the claim 1, wherein be provided with partition in the heat exchange unit in decomposition of hydrate device
Formula heat exchange equipment, hot fluid are walked tube side and are heated by coil form to hydrate slurry.
10. acidity device of air described in accordance with the claim 1, wherein heat exchange equipment in the decomposition unit in decomposition of hydrate device
Coil pipe between be arranged multiple groups hydraulic barrier.
11. acidity device of air described in accordance with the claim 1, wherein the regeneration of the decomposition unit bottom in decomposition of hydrate device
The outlet of hydrate working solution divides two-way, wherein connecting all the way through pipeline with the filter washing water inlet, by decomposed unit bottom
The regeneration hydrate working solution of discharge is used as interior circulating cleaning fluid, the regeneration hydration used as interior circulating cleaning fluid
Object working solution volume flow Zhan always regenerates 1/5~1, preferably the 1/3~1/2 of hydrate working solution volume flow.
12. a kind of hydration method separates sour gas technique, the technique includes following content:
(1) raw material sour gas enters hydration reactor, reacts with hydrate working solution, the H in sour gas2S gas and hydration
The reaction of object working solution, mutually forms hydrate slurry, CO into hydrate2In gas phase enrichment, and hydration reactor is discharged；
(2) obtained in step (1) to be rich in H2The hydrate slurry of S gas enters decomposition of hydrate device, in decomposition of hydrate device
Lonely liquid and rich hydrate phase slurries are obtained after the processing of slurries separative unit, lonely liquid enters the lonely liquid reservoir of lower section；
(3) obtain the cleaned liquid effect of rich hydrate phase slurries in step (2) and enter decomposition unit, in regenerated liquid reservoir with
Product liquid from absorbing reaction device exchanges heat, and is passed through stripping gas counter current contacting with decomposition unit bottom, and decomposition releases
H2S gas, while decomposition of hydrate obtains reproduction operation liquid, regeneration hydrate working solution is mixed with lonely liquid and the processing that cools down
Afterwards, hydration reactor is returned to be recycled；
(4) H that step (3) obtains2S gas enters absorbing reaction device, is reacted with lye, treated exhaust emissions, obtains
Product liquid divide two-way, the first via enters decomposition of hydrate device as absorbing reaction device is returned after heat source heat exchange, and the second tunnel enters
Products pot.
13. technique according to claim 12, wherein the pressure of step (1) described sour gas and the behaviour of hydration reactor
Match as pressure, acid atmospheric pressure is 0.1Mpa~3.0Mpa, preferably 0.3Mpa~1.5Mpa, sour gas insufficient pressure
When, it is pressurized by compressor.
14. technique according to claim 12, wherein step (1) the hydrate working solution dosage and sour gas volume
Than for 5~100L/m3, preferably 10~50L/m3。
15. technique according to claim 12, wherein the operating condition of hydration reactor are as follows: pressure 0.1Mpa~
3.0Mpa, preferably 0.3Mpa~1.5Mpa, 0~15 DEG C of temperature, preferably 3~10 DEG C.
16. technique according to claim 12, wherein in step (1) described hydration reactor, hydrate slurry refers to shape
The mixed solution of hydrate working solution is generated at hydrate and unreacted, reaction controlling hydrate accounts for the volume in hydrate slurry
Than being 30%~80%, preferably 50%~70%.
17. technique according to claim 12, wherein the operating condition of step (2) the decomposition of hydrate device are as follows: pressure
0.02Mpa~2.0Mpa, preferably 0.05Mpa~1.0Mpa, 0~10 DEG C of slurries separative unit temperature, decomposition unit temperature 10~
40℃。
18. technique according to claim 12, wherein step (3) described stripping gas is not occur with following process process
The arbitrary gas of reaction, such as nitrogen, inert gas.
19. technique according to claim 12, wherein step (3) described stripping gas is the decomposition gas that decomposition unit obtains.
20. technique according to claim 12, wherein step (3) the regeneration hydrate working solution is with lonely liquid through cold
But temperature control is at 0~15 DEG C after, preferably 3~10 DEG C, returns to hydration reactor and is recycled.
21. technique according to claim 12, wherein the absorbing reaction device operating condition are as follows: pressure 0.02Mpa~
2.0Mpa, preferably 0.1Mpa~1.0Mpa, 70~95 DEG C of temperature, preferably 80~90 DEG C.
22. technique according to claim 12, wherein the lye is NaOH solution, and mass concentration is 20%~60%, excellent
It is selected as 32%~48%.
23. technique according to claim 12, wherein step (4) the product liquid that absorbing reaction device reacts out
Divide two-way, the first via enters decomposition of hydrate device and uses as heat source, and the second tunnel enters products pot, the first via and the second tunnel
Product flow quantity ratio be 20/1~1/1, preferably 10/1~2/1.
24. technique according to claim 12, wherein the decomposition of hydrate device is using the hydrate having the following structure
Decomposer, the decomposition of hydrate device include slurries separative unit and decomposition unit, the slurries separative unit and decomposition unit
It is connected to by interface channel；The slurries separative unit through filter screen separator component be divided into up and down two parts, top from top to bottom according to
Secondary to be provided with hydrate slurry entrance, filter washing water inlet, interface channel interface, lower part is lonely liquid reservoir, liquid storage trench bottom
Equipped with cold purified liquor outlet；The decomposition unit be disposed with from top to bottom decomposition of hydrate gas outlet, interface channel interface and
Regenerated liquid reservoir is disposed with heat exchange unit, stripping gas entrance, regeneration hydrate work in regenerated liquid reservoir from top to bottom
Make liquid outlet.
25. according to the technique described in claim 24, wherein the interface channel is horizontally disposed or inclines at an angle
Tiltedly setting makes slurries separative unit interface channel interface be higher than decomposition unit interface channel interface, inclination angle when being obliquely installed
Degree and horizontal plane are at 10 °~60 °, preferably 15 °~45 °.
26. technique according to claim 11, wherein the filter screen separator component level setting is either at an angle
It is obliquely installed, the upper plane of filter screen separator component will keep arranging with the lower plane of interface channel in same plane.
27. according to the technique of claim 24, wherein the lonely liquid reservoir liquid holdup is the 1/3~2/ of liquid storage sump volume
3。
28. according to the technique of claim 24, wherein the regenerated liquid reservoir liquid holdup is the 1/2~5/ of liquid storage sump volume
6。
29. according to the technique of claim 24, wherein be provided with wall-type heat exchange equipment in the heat exchange unit, hot fluid is walked
Tube side heats hydrate slurry by coil form.
30. according to the technique of claim 29, wherein multiple groups baffling is arranged in the decomposition unit between the coil pipe of heat exchange equipment and keeps off
Plate.
31. according to the technique of claim 24, wherein the regeneration hydrate working solution outlet of the decomposition unit bottom is divided to two
Road, wherein connecting all the way through pipeline with the filter washing water inlet, the regeneration hydrate that decomposed unit bottom is discharged works
Liquid is used as interior circulating cleaning fluid, and the regeneration hydrate working solution volume flow Zhan used as interior circulating cleaning fluid is total
Regenerate 1/5~1, preferably the 1/3~1/2 of hydrate working solution volume flow.
32. technique according to claim 11, wherein the hydrate working solution is the aqueous solution added with auxiliary agent,
The auxiliary agent includes auxiliary agent A, the auxiliary agent A be lauryl sodium sulfate, sodium dodecylbenzenesulfonate, linear alkyl sodium sulfonate,
One or more of alkyl polyglycoside, mass fraction 0.005%~1.0%, 0.01%~0.5 % of preferred mass score.
33. according to the technique of claim 32, wherein add auxiliary agent B in the hydrate working solution, the auxiliary agent B is coal
One or more of oil, diesel oil and silicone oil, the additive amount of auxiliary agent B are 1/5~2/ with the volume ratio of water in hydrate working solution
1, preferably 1/3~1/1.
34. according to the technique of claim 33, wherein emulsifier is added when adding auxiliary agent B in the hydrate working solution,
Selected emulsifier is hydrophilic emulsifier, forms Water-In-Oil (o/w) type lotion or lipophilic emulsifier, forms water
Oily (w/o) type lotion is wrapped, the mole fraction of water is 0.5%~3% in the additive amount and hydrate working solution of emulsifier.
35. according to claim 34 technique, wherein include auxiliary agent C in the hydrate working solution, the auxiliary agent C is N- first
One or more of base pyrrolidones, propene carbonate, sulfolane, N- N-formyl morpholine N, polyethylene glycol, the matter of the auxiliary agent C
Measuring score is 2%~30%, preferably 5%~20 %.
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| CN114522524A (en) * | 2022-03-25 | 2022-05-24 | 广州市粤佳气体有限公司 | Device for separating gas by hydration method |
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| WO2010137399A1 (en) * | 2009-05-26 | 2010-12-02 | 三井造船株式会社 | Device and method for separating gases to be separated |
| CN103480275A (en) * | 2013-09-17 | 2014-01-01 | 常州大学 | Device and method for acid gas concentration, desalination and separation after doctor solution regeneration |
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