CN106554833A - A kind of removing of hydrogen sulfide in natural gas and recycling processing method - Google Patents
A kind of removing of hydrogen sulfide in natural gas and recycling processing method Download PDFInfo
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- CN106554833A CN106554833A CN201510615879.5A CN201510615879A CN106554833A CN 106554833 A CN106554833 A CN 106554833A CN 201510615879 A CN201510615879 A CN 201510615879A CN 106554833 A CN106554833 A CN 106554833A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- Chemical Kinetics & Catalysis (AREA)
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
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Abstract
The present invention relates to a kind of removing of hydrogen sulfide in natural gas and recycling processing method, comprise the steps：First, under a certain pressure, natural gas containing hydrogen sulfide is pressed into into the shell side of hollow fiber hydrophobic membrane unit, with cold water as absorbing liquid, make cold water in the tube side of hollow fiber hydrophobic membrane unit and the natural gas reverse flow containing hydrogen sulfide, hydrogen sulfide in natural gas penetrates film and enters in water, forms the water containing hydrogen sulfide；Secondly, the water containing hydrogen sulfide is pumped into negative pressure desulfurization unit carries out negative pressure desulfurization, produces hydrogen sulfide and desulfurization water outlet；Finally, the hydrogen sulfide that negative pressure desulfurization unit is produced is pumped into absorption tower carries out alkali liquor absorption, and the alkali liquor is sodium hydroxide solution, reaction solution body NaHS product, so as to realize removing and the resource of hydrogen sulfide in natural gas.Technical equipment according to the present invention is simple, operation maintenance easy, strong environmental adaptability, desulfuration efficiency are high, be capable of achieving modularized processing, operating cost reduces.
Description
Technical field
The present invention relates to natural gas purification field, specifically a kind of hydrogen sulfide in natural gas it is de-
Except and recycling processing method.Hydrophobic membrane separation technique+negative pressure desulfurization technology+alkali liquor is utilized espespecially
Absorption techniqueses remove hydrogen sulfide in natural gas and make the processing method of its resource.
Background technology
With the development of gas industry, high sulfur Gas Fields continuously emerge, containing big in natural gas
Amount H2S gases, due to H2When S gases run into condensed water, pipeline and container band can be not only given
Carry out general corrosion, and stress-corrosion cracking due to sulphide inclusion can be caused.Additionally, CO2Too high levels
The calorific value of natural gas can be made not reach requirement.Therefore, various countries have to quality of natural gas accordingly
Purification standard.Gas purifying process generally comprises the techniques such as selexol process, decarburization, dehydration.
With regard to manage it is defeated for, health of human body safety is mainly supplied and taken into account according to stable equilibrium and is determined each
Item specific targets, H in general natural gas2S contents should be less than 20mg/m3, CO2Content most
It is less than well 2%～3%.
Selexol process is generally divided into two big class of dry and wet.Dry desulfurization is due to desulfurizing agent one
As can not regenerate, industrially using less.Wet desulphurization treating capacity is big, and operation is continuous, fits
For the process of high sulfur-containing natural gas, the purification of natural gas and refinery gas is now widely used for,
Chemical absorption method, Physical Absorption method and blended absorbent method can be divided into.
For at present, chemical absorption method (referring to alcohol amine absorption process) is that selexol process technique is most normal
Method.The substantially technological process of chemical absorption method is：Containing hydrogen sulfide (H2S original)
Material gas enters absorption tower from bottom, and (lean amine is molten for the absorbing liquid entered at the top of unstripped gas and absorption tower
Liquid) inversely contact, the hydrogen sulfide in unstripped gas is constantly absorbed by lean amine aqueous solution, and lean amine aqueous solution turns
Rich amine solution is changed to, rich amine solution enters desorber solution after heat exchanger with the heat exchange of lean amine aqueous solution
Regeneration is inhaled, the lean amine aqueous solution after desorbing is recycled.In the technique, absorbing liquid (the lean amine
Solution) for alkanolamine solution, its desorption temperature is required higher than 105 DEG C, needs to consume a large amount of heat energy.
Additionally, the equipment corrosion that the loss of alcohol amine solvent, foaming and degraded and degrading solvent cause is
The subject matter that the technique presently, there are.Additionally, absorption tower and desorber floor space are larger,
The yards such as the oil gas field being limited especially for place are less suitable for.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of natural gas
The removing of middle hydrogen sulfide and recycling processing method, using hydrophobic membrane separation technique+negative pressure desulfurization
Technology+alkali liquor absorption technology removing hydrogen sulfide in natural gas simultaneously makes its resource.
To reach object above, the present invention is adopted the technical scheme that：
A kind of removing of hydrogen sulfide in natural gas and recycling processing method, it is characterised in that bag
Include following steps：
First, under a certain pressure, will be the press-in doughnut of the natural gas containing hydrogen sulfide hydrophobic
The shell side of film unit, with cold water as absorbing liquid, makes cold water in the pipe of hollow fiber hydrophobic membrane unit
In journey and the natural gas reverse flow containing hydrogen sulfide, the hydrogen sulfide in natural gas penetrates film and enters
Enter in water, form the water containing hydrogen sulfide；
Secondly, the water containing hydrogen sulfide is pumped into negative pressure desulfurization unit carries out negative pressure desulfurization, produces
Hydrogen sulfide and desulfurization water outlet；
Finally, the hydrogen sulfide that negative pressure desulfurization unit is produced is pumped into absorption tower carries out alkali liquor absorption,
The alkali liquor be sodium hydroxide solution, reaction solution body NaHS product, so as to realize day
The removing of hydrogen sulfide and resource in right gas.
On the basis of above-mentioned technical proposal, the natural gas through removing hydrogen sulfide concentrates conveying to make
With.
On the basis of above-mentioned technical proposal, the desulfurization water outlet of negative pressure desulfurization unit returns to hollow
The hydrophobic film unit of fiber is recycled as absorbing liquid.
On the basis of above-mentioned technical proposal, it is, under 0.1～0.4MPa, sulfur will to be contained in pressure
The natural gas for changing hydrogen is pressed into the shell side of hollow fiber hydrophobic membrane unit.
On the basis of above-mentioned technical proposal, the membrane material of the hollow fiber hydrophobic membrane unit is
Polypropylene, membrane aperture are 0.1～0.2 μm.
On the basis of above-mentioned technical proposal, hollow fiber hydrophobic membrane unit is set according to processing requirement
Count into multistage form.
On the basis of above-mentioned technical proposal, the temperature of the absorbing liquid is 5～15 DEG C, water inlet
Flow velocity is 0.5～1.0m/s.
On the basis of above-mentioned technical proposal, the negative pressure of negative pressure desulfurization unit adopts dry vacuum pump
Formed.
On the basis of above-mentioned technical proposal, the operation negative pressure of the negative pressure desulfurization unit is
- 0.05～-0.09MPa.
On the basis of above-mentioned technical proposal, the inflow temperature of negative pressure desulfurization unit is
35～45 DEG C.
On the basis of above-mentioned technical proposal, the negative pressure desulfurization unit arranges circulating pump and is given up
Water circulation, reflux ratio are 2～5:1.
On the basis of above-mentioned technical proposal, the retention time of sewage of the negative pressure desulfurization unit is
20～30min.
On the basis of above-mentioned technical proposal, the hollow fiber hydrophobic membrane unit and negative pressure desulfurization
Heat exchanger is provided between unit,
The sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is before into negative pressure desulfurization unit and negative
The desulfurization water outlet of desulfurization unit is pressed before into hollow fiber hydrophobic membrane unit, by heat exchanger
Heat exchange is realized in heat exchange.
On the basis of above-mentioned technical proposal, the sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is passed through
After exchanger heat is exchanged, if the inflow temperature of predetermined negative pressure desulfurization unit can not be reached,
Pipeline heater need to be equipped with or heating tape continues heating.
On the basis of above-mentioned technical proposal, the desulfurization water outlet of negative pressure desulfurization unit is through heat exchanger
After heat exchange, if the temperature of predetermined absorbing liquid can not be reached, need to be equipped with cooling-water machine continuation
Cooling.
On the basis of above-mentioned technical proposal, in the absorption tower, solution temperature is 20～35 DEG C.
On the basis of above-mentioned technical proposal, the sodium hydroxide solution mass concentration is
30%～40%.
On the basis of above-mentioned technical proposal, absorption tower water outlet enters surge tank, and analysis detection is slow
The solution rushed in tank is mainly sodium sulfide solution and then returns to absorption tower, and predominantly NaHS is molten
Liquid then does production marketing.
The removing of hydrogen sulfide in natural gas of the present invention and recycling processing method, using not
With the difference of gas dissolubility in water, first, with water as absorbing liquid, using hydrophobic membrane by day
So the hydrogen sulfide absorption in gas is in the water of film opposite side；Secondly, the sulfur-bearing of membrane permeation side is gone out
Water is by out and being collected the hydrogen sulfide stripping in water using negative pressure desulfurization technology；Finally, receive
The hydrogen sulfide of collection carries out alkali liquor absorption into absorption tower, forms NaHS product, realizes natural
The removing of hydrogen sulfide and resource target in gas.
The removing of hydrogen sulfide in natural gas of the present invention and recycling processing method, using water
For absorbing liquid, environmental protection, in solving natural gas chemistry absorption process sulfur removal technology, hydramine is adopted
Equipment corrosion that solvent loss, foaming and degraded and the degrading solvent that absorption causes causes etc. is asked
Topic, while realizing the resource of hydrogen sulfide, and reduces the floor space of equipment, saves use
Ground, for modularized processing can be realized in the area that place is limited.
Description of the drawings
The present invention has drawings described below：
The process chart of Fig. 1 present invention.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing.
As shown in figure 1, the removing of hydrogen sulfide in natural gas of the present invention and recycling treatment
Method, comprises the steps：
First, under a certain pressure, the natural gas containing hydrogen sulfide (sulfur-containing gas) is pressed
Enter the shell side of hollow fiber hydrophobic membrane unit (membrane module), with cold water as absorbing liquid, make cold water
Hollow fiber hydrophobic membrane unit (membrane module) tube side (i.e. doughnut fenestra) in and contain
There is the natural gas reverse flow of hydrogen sulfide, the hydrogen sulfide in natural gas penetrates film and enters into water
In, form the water containing hydrogen sulfide (sulfur-bearing water outlet)；
Secondly, the water containing hydrogen sulfide is pumped into into (pump into by intake pump) negative pressure desulfurization unit
Negative pressure desulfurization is carried out, hydrogen sulfide and desulfurization water outlet is produced；
Finally, the hydrogen sulfide that negative pressure desulfurization unit is produced is pumped into into (pump into by air intake pump) suction
Receiving tower carries out alkali liquor absorption, and the alkali liquor is sodium hydroxide solution, the hydrogenation of reaction solution body sulfur
Sodium product, so as to realize removing and the resource of hydrogen sulfide in natural gas.Through removing hydrogen sulfide
Natural gas (desulphurised natural gas) concentrate conveying use.
On the basis of above-mentioned technical proposal, the desulfurization water outlet of negative pressure desulfurization unit returns to hollow
The hydrophobic film unit of fiber is recycled as absorbing liquid.
On the basis of above-mentioned technical proposal, it is, under 0.1～0.4MPa, sulfur will to be contained in pressure
Change the natural gas (sulfur-containing gas) press-in hollow fiber hydrophobic membrane unit (membrane module) of hydrogen
Shell side.
On the basis of above-mentioned technical proposal, the membrane material of the hollow fiber hydrophobic membrane unit is
Polypropylene, membrane aperture are 0.1～0.2 μm.
On the basis of above-mentioned technical proposal, hollow fiber hydrophobic membrane unit can according to processing requirement
It is designed to multistage form.
On the basis of above-mentioned technical proposal, the temperature of the absorbing liquid is 5～15 DEG C, water inlet
Flow velocity is 0.5～1.0m/s.
On the basis of above-mentioned technical proposal, the negative pressure of negative pressure desulfurization unit adopts dry vacuum pump
Formed.
On the basis of above-mentioned technical proposal, the operation negative pressure of the negative pressure desulfurization unit is
- 0.05～-0.09MPa.
On the basis of above-mentioned technical proposal, the inflow temperature of negative pressure desulfurization unit is
35～45 DEG C.
On the basis of above-mentioned technical proposal, the negative pressure desulfurization unit arranges circulating pump and is given up
Water circulation, reflux ratio are 2～5:1.
On the basis of above-mentioned technical proposal, the retention time of sewage of the negative pressure desulfurization unit is
20～30min.
On the basis of above-mentioned technical proposal, the hollow fiber hydrophobic membrane unit and negative pressure desulfurization
Heat exchanger is provided between unit,
The sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is before into negative pressure desulfurization unit and negative
The desulfurization water outlet of desulfurization unit is pressed before into hollow fiber hydrophobic membrane unit, by heat exchanger
Heat exchange is realized in heat exchange.
On the basis of above-mentioned technical proposal, the sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is passed through
After exchanger heat is exchanged, if the inflow temperature of predetermined negative pressure desulfurization unit can not be reached,
Pipeline heater need to be equipped with or heating tape continues heating.
On the basis of above-mentioned technical proposal, the desulfurization water outlet of negative pressure desulfurization unit is through heat exchanger
After heat exchange, if the temperature of predetermined absorbing liquid can not be reached, need to be equipped with cooling-water machine continuation
Cooling.
On the basis of above-mentioned technical proposal, in the absorption tower, solution temperature is 20～35 DEG C.
On the basis of above-mentioned technical proposal, the sodium hydroxide solution mass concentration is
30%～40%.
On the basis of above-mentioned technical proposal, absorption tower water outlet enters surge tank, and analysis detection is slow
The solution rushed in tank is mainly sodium sulfide solution and then returns to absorption tower, and predominantly NaHS is molten
Liquid then does production marketing.
The present invention with the essential distinction of prior art is：For chemistry is adopted in prior art
Solvent loss, foaming and degraded and solvent that hydrogen sulfide in absorption process removing natural gas is present
The problems such as equipment corrosion that degraded causes, the present invention, are removed with water as absorbing liquid using hydrophobic membrane
Hydrogen sulfide in natural gas, and its resource is made by alkali liquor absorption.
By using the technology, realizing the low energy consumption of the hydrogen sulfide in natural gas, high efficiency and taking off
Except and its resource.Compared to the prior art, technology of the invention solves existing chemical absorbing
Technology desulfurization exist equipment is huge, solvent loss, foaming and degrade and degrading solvent causes
Equipment corrosion the problems such as, technical equipment according to the present invention is simple, operation maintenance easily, ring
Border is adaptable, desulfuration efficiency is high, be capable of achieving modularized processing, operating cost reduces.
The removing of hydrogen sulfide in natural gas of the present invention and recycling processing method, its beneficial effect
It is really：
1st, removing and the resource of hydrogen sulfide in natural gas are carried out using the method for the present invention, is kept away
The absorption and desorption using hydramine chemical absorbing liquid are exempted from, environmental protection is solved and adopts hydramine
The equipment that solvent loss, foaming and degraded and the degrading solvent that chemical absorbing liquid causes causes is rotten
The problems such as erosion.
2nd, method of the present invention Processes and apparatus is simple, efficient, and operating cost is low, automatization
Ability is strong, and equipment takes up an area less, is particularly suited for place and the restricted area of other external conditions.
Natural gas after the inventive method process, hydrogen sulfide content are less than 20mg/m3, can
To meet restriction index of the natural gas to hydrogen sulfide, the liquid NaHS product that technique is produced is full
Sufficient industrial products sell standard.
It is below some specific embodiments.
Embodiment 1
Hydrogen sulfide volume content in certain natural gas is 10%.
Process step is as follows：Under pressure 0.1MPa, the natural gas containing hydrogen sulfide is pressed into
Aperture is the shell side of 0.2 μm of polypropylene hollow fiber hydrophobic membrane unit membrane module,
With cold water that temperature is 5 DEG C as absorbing liquid so as in polypropylene hollow fiber hydrophobic membrane list
The natural gas reverse flow of hydrogen sulfide is contained within the tube side of first membrane module with shell side, in natural gas
Hydrogen sulfide penetrate film and enter in absorbing liquid, the chilled water flow velocity in tube side is 0.5m/s,
The sulfur-bearing water outlet of hydrophobic membrane unit tube side is heated using pipeline after exchanger heat exchange
Device is heated to 45 DEG C, and pumping into negative pressure desulfurization unit by intake pump carries out negative pressure desulfurization,
The operating condition of negative pressure desulfurization is：Operation negative pressure -0.05MPa, hydraulic detention time
20min, the reflux ratio of circulating pump is 5:1.
The desulfurization water outlet of negative pressure desulfurization unit returns to hydrophobic film unit and makes as absorbing liquid circulation
With.
The hydrogen sulfide that negative pressure desulfurization unit is extracted out is into the hydrogen that absorption tower mass concentration is 30%
Sodium hydroxide solution is absorbed, and the solution temperature in absorption tower is 35 DEG C, reaction solution body
NaHS product, so as to realize removing and the resource of hydrogen sulfide in natural gas.
Wherein, the desulfurization water outlet of negative pressure desulfurization unit through exchanger heat exchange after, if can not
Predetermined temperature is reached, cooling-water machine can be equipped with and continued to be cooled to that hydrophobic film unit limits enters water temperature
Degree.By hydrophobic film unit and negative pressure desulfurization unit, hydrogen sulfide is realized using water as absorption
The absorption and desorption process of liquid.
The hydrogen sulfide content in natural gas after above-mentioned steps process is less than 20mg/m3, can
To meet restriction index of the natural gas to hydrogen sulfide.Natural gas through removing hydrogen sulfide concentrates defeated
Use is sent, the liquid NaHS product for generating is reacted and is met industrial products sale standard.
Embodiment 2
Hydrogen sulfide volume content in certain natural gas is 12%.
Process step is as follows：Under pressure 0.2MPa, the natural gas containing hydrogen sulfide is pressed into
Aperture is the shell side of 0.15 μm of polypropylene hollow fiber hydrophobic membrane unit membrane module,
With cold water that temperature is 15 DEG C as absorbing liquid so as in polypropylene hollow fiber hydrophobic membrane
In the tube side of unit membrane module and the natural gas reverse flow containing hydrogen sulfide, the sulfur in natural gas
Change hydrogen penetrates film and enters in absorbing liquid, and the chilled water flow velocity in tube side is 1.0m/s,
The sulfur-bearing water outlet of hydrophobic membrane unit tube side is heated using pipeline after exchanger heat exchange
Device is heated to 40 DEG C, and pumping into negative pressure desulfurization unit by intake pump carries out negative pressure desulfurization,
The operating condition of negative pressure desulfurization is：Operation negative pressure -0.06MPa, hydraulic detention time
25min, the reflux ratio of circulating pump is 4:1.
The desulfurization water outlet of negative pressure desulfurization unit returns to hydrophobic film unit and makes as absorbing liquid circulation
With.
The hydrogen sulfide that negative pressure desulfurization unit is extracted out is into the hydrogen that absorption tower mass concentration is 33%
Sodium hydroxide solution is absorbed, and the solution temperature in absorption tower is 30 DEG C, reaction solution body
NaHS product, so as to realize removing and the resource of hydrogen sulfide in natural gas.
Wherein, the desulfurization water outlet of negative pressure desulfurization unit through exchanger heat exchange after, if can not
Predetermined temperature is reached, cooling-water machine can be equipped with and continued to be cooled to that hydrophobic film unit limits enters water temperature
Degree.By hydrophobic film unit and negative pressure desulfurization unit, hydrogen sulfide is realized using water as absorption
The absorption and desorption process of liquid.
The hydrogen sulfide content in natural gas after above-mentioned steps process is less than 20mg/m3, can
To meet restriction index of the natural gas to hydrogen sulfide.Natural gas through removing hydrogen sulfide concentrates defeated
Use is sent, the liquid NaHS product for generating is reacted and is met industrial products sale standard.
Embodiment 3
Hydrogen sulfide volume content in certain natural gas is 15%.
Process step is as follows：Under pressure 0.4MPa, the natural gas containing hydrogen sulfide is pressed into
Aperture is the shell side of 0.1 μm of polypropylene hollow fiber hydrophobic membrane unit membrane module,
With cold water that temperature is 8 DEG C as absorbing liquid so as in polypropylene hollow fiber hydrophobic membrane list
In the tube side of first membrane module and the natural gas reverse flow containing hydrogen sulfide, the sulfuration in natural gas
Hydrogen penetrates film and enters in absorbing liquid, and the chilled water flow velocity in tube side is 0.8m/s,
The sulfur-bearing water outlet of hydrophobic membrane unit tube side is heated using pipeline after exchanger heat exchange
Device is heated to 35 DEG C, and pumping into negative pressure desulfurization unit by intake pump carries out negative pressure desulfurization,
The operating condition of negative pressure desulfurization is：Operation negative pressure -0.08MPa, hydraulic detention time
28min, the reflux ratio of circulating pump is 3:1.
The desulfurization water outlet of negative pressure desulfurization unit returns to hydrophobic film unit and makes as absorbing liquid circulation
With.
The hydrogen sulfide that negative pressure desulfurization unit is extracted out is into the hydrogen that absorption tower mass concentration is 35%
Sodium hydroxide solution is absorbed, and the solution temperature in absorption tower is 25 DEG C, reaction solution body
NaHS product, so as to realize removing and the resource of hydrogen sulfide in natural gas.
Wherein, the desulfurization water outlet of negative pressure desulfurization unit through exchanger heat exchange after, if can not
Predetermined temperature is reached, cooling-water machine can be equipped with and continued to be cooled to that hydrophobic film unit limits enters water temperature
Degree.By hydrophobic film unit and negative pressure desulfurization unit, hydrogen sulfide is realized using water as absorption
The absorption and desorption process of liquid.
The hydrogen sulfide content in natural gas after above-mentioned steps process is less than 20mg/m3, can
To meet restriction index of the natural gas to hydrogen sulfide.Natural gas through removing hydrogen sulfide concentrates defeated
Use is sent, the liquid NaHS product for generating is reacted and is met industrial products sale standard.
Embodiment 4
Hydrogen sulfide volume content in certain natural gas is 18%.
Process step is as follows：Under pressure 0.4MPa, the natural gas containing hydrogen sulfide is pressed into
Aperture is the shell side of 0.1 μm of polypropylene hollow fiber hydrophobic membrane unit membrane module,
With cold water that temperature is 10 DEG C as absorbing liquid so as in polypropylene hollow fiber hydrophobic membrane
In the tube side of unit membrane module and the natural gas reverse flow containing hydrogen sulfide, the sulfur in natural gas
Change hydrogen penetrates film and enters in absorbing liquid, and the chilled water flow velocity in tube side is 0.7m/s,
The sulfur-bearing water outlet of hydrophobic membrane unit tube side is heated using pipeline after exchanger heat exchange
Device is heated to 38 DEG C, and pumping into negative pressure desulfurization unit by intake pump carries out negative pressure desulfurization,
The operating condition of negative pressure desulfurization is：Operation negative pressure -0.09MPa, hydraulic detention time
30min, the reflux ratio of circulating pump is 2:1.
The desulfurization water outlet of negative pressure desulfurization unit returns to hydrophobic film unit and makes as absorbing liquid circulation
With.
The hydrogen sulfide that negative pressure desulfurization unit is extracted out is into the hydrogen that absorption tower mass concentration is 40%
Sodium hydroxide solution is absorbed, and the solution temperature in absorption tower is 20 DEG C, reaction solution body
NaHS product, so as to realize removing and the resource of hydrogen sulfide in natural gas.
Wherein, the desulfurization water outlet of negative pressure desulfurization unit through exchanger heat exchange after, if can not
Predetermined temperature is reached, cooling-water machine can be equipped with and continued to be cooled to that hydrophobic film unit limits enters water temperature
Degree.By hydrophobic film unit and negative pressure desulfurization unit, hydrogen sulfide is realized using water as absorption
The absorption and desorption process of liquid.
The hydrogen sulfide content in natural gas after above-mentioned steps process is less than 20mg/m3, can
To meet restriction index of the natural gas to hydrogen sulfide.Natural gas through removing hydrogen sulfide concentrates defeated
Use is sent, the liquid NaHS product for generating is reacted and is met industrial products sale standard.
The preferable possible embodiments of the present invention are the foregoing is only, not thereby limits to the present invention's
The scope of the claims, therefore the equivalence changes made by every utilization description of the invention and accompanying drawing content,
It is contained in protection scope of the present invention.
The content not being described in detail in this specification belongs to known in professional and technical personnel in the field
Prior art.
Claims (18)
1. a kind of removing of hydrogen sulfide in natural gas and recycling processing method, it is characterised in that
Comprise the steps：
First, under a certain pressure, will be the press-in doughnut of the natural gas containing hydrogen sulfide hydrophobic
The shell side of film unit, with cold water as absorbing liquid, makes cold water in the pipe of hollow fiber hydrophobic membrane unit
In journey and the natural gas reverse flow containing hydrogen sulfide, the hydrogen sulfide in natural gas penetrates film and enters
Enter in water, form the water containing hydrogen sulfide；
Secondly, the water containing hydrogen sulfide is pumped into negative pressure desulfurization unit carries out negative pressure desulfurization, produces
Hydrogen sulfide and desulfurization water outlet；
Finally, the hydrogen sulfide that negative pressure desulfurization unit is produced is pumped into absorption tower carries out alkali liquor absorption,
The alkali liquor be sodium hydroxide solution, reaction solution body NaHS product, so as to realize day
The removing of hydrogen sulfide and resource in right gas.
2. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：Natural gas through removing hydrogen sulfide concentrates conveying to use.
3. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The desulfurization water outlet of negative pressure desulfurization unit returns to hollow fiber hydrophobic membrane list
Unit is recycled as absorbing liquid.
4. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：It is under 0.1～0.4MPa, by the natural gas containing hydrogen sulfide in pressure
The shell side of press-in hollow fiber hydrophobic membrane unit.
5. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The membrane material of the hollow fiber hydrophobic membrane unit be polypropylene, fenestra
Footpath is 0.1～0.2 μm.
6. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：Hollow fiber hydrophobic membrane unit is designed to multistage shape according to processing requirement
Formula.
7. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The temperature of the absorbing liquid is 5～15 DEG C, and water inlet flow velocity is
0.5～1.0m/s.
8. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The negative pressure of negative pressure desulfurization unit is formed using dry vacuum pump.
9. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The operation negative pressure of the negative pressure desulfurization unit is -0.05～-0.09MPa.
10. the removing of hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The inflow temperature of negative pressure desulfurization unit is 35～45 DEG C.
The removing of 11. hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The negative pressure desulfurization unit arranges circulating pump and carries out waste water circulation, flows back
Than for 2～5:1.
The removing of 12. hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The retention time of sewage of the negative pressure desulfurization unit is 20～30min.
The removing of 13. hydrogen sulfide in natural gas as claimed in claim 2 and recycling treatment side
Method, it is characterised in that：It is provided between the hollow fiber hydrophobic membrane unit and negative pressure desulfurization unit and changes
Hot device,
The sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is before into negative pressure desulfurization unit and negative
The desulfurization water outlet of desulfurization unit is pressed before into hollow fiber hydrophobic membrane unit, by heat exchanger
Heat exchange is realized in heat exchange.
The removing of 14. hydrogen sulfide in natural gas as claimed in claim 13 and recycling treatment
Method, it is characterised in that：The sulfur-bearing water outlet of hollow fiber hydrophobic membrane unit is handed over through exchanger heat
After changing, if the inflow temperature of predetermined negative pressure desulfurization unit can not be reached, need to be equipped with pipeline
Heater or heating tape continue heating.
The removing of 15. hydrogen sulfide in natural gas as claimed in claim 13 and recycling treatment
Method, it is characterised in that：The desulfurization water outlet of negative pressure desulfurization unit through exchanger heat exchange after,
If the temperature of predetermined absorbing liquid can not be reached, need to be equipped with cooling-water machine continuation cooling.
The removing of 16. hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：In the absorption tower, solution temperature is 20～35 DEG C.
The removing of 17. hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：The sodium hydroxide solution mass concentration is 30%～40%.
The removing of 18. hydrogen sulfide in natural gas as claimed in claim 1 and recycling treatment side
Method, it is characterised in that：Absorption tower water outlet enters surge tank, the solution in analysis detection surge tank
Predominantly sodium sulfide solution then returns to absorption tower, and predominantly sodium hydrosulfide then does product pin
Sell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN1240672A (en) * | 1999-04-26 | 2000-01-12 | 浙江大学膜分离工程联合公司 | Process for removing components from mixed gas with microporous membrane of hollow fibres |
| US6017501A (en) * | 1997-12-26 | 2000-01-25 | Marathon Oil Company | Disposal of hydrogen sulfide gas by conversion to sulfate ions in an aqueous solution |
| CN1785480A (en) * | 2005-11-17 | 2006-06-14 | 江苏工业学院 | Membrane adsorption natural gas desulfur method |
| CN101584960A (en) * | 2008-05-22 | 2009-11-25 | 青岛生物能源与过程研究所 | Separator and separation and purification method of gas-liquid phase absorbing membrane |
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| US6017501A (en) * | 1997-12-26 | 2000-01-25 | Marathon Oil Company | Disposal of hydrogen sulfide gas by conversion to sulfate ions in an aqueous solution |
| CN1240672A (en) * | 1999-04-26 | 2000-01-12 | 浙江大学膜分离工程联合公司 | Process for removing components from mixed gas with microporous membrane of hollow fibres |
| CN1785480A (en) * | 2005-11-17 | 2006-06-14 | 江苏工业学院 | Membrane adsorption natural gas desulfur method |
| CN101584960A (en) * | 2008-05-22 | 2009-11-25 | 青岛生物能源与过程研究所 | Separator and separation and purification method of gas-liquid phase absorbing membrane |
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