CN101591580B - Desulfuration method of environmental-friendly liquefied petroleum gas - Google Patents
Desulfuration method of environmental-friendly liquefied petroleum gas Download PDFInfo
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- CN101591580B CN101591580B CN200810113635.7A CN200810113635A CN101591580B CN 101591580 B CN101591580 B CN 101591580B CN 200810113635 A CN200810113635 A CN 200810113635A CN 101591580 B CN101591580 B CN 101591580B
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- 239000003915 liquefied petroleum gas Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 65
- 229910052717 sulfur Inorganic materials 0.000 claims description 38
- 239000011593 sulfur Substances 0.000 claims description 38
- 239000005864 Sulphur Substances 0.000 claims description 28
- 210000004379 membrane Anatomy 0.000 claims description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 238000007670 refining Methods 0.000 claims description 20
- 239000012466 permeate Substances 0.000 claims description 15
- 230000023556 desulfurization Effects 0.000 claims description 13
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 10
- 210000002469 basement membrane Anatomy 0.000 claims description 8
- YVUUNVFJBRJLPO-UHFFFAOYSA-N buta-1,3-dien-1-ol prop-2-enenitrile Chemical compound C(C=C)#N.OC=CC=C YVUUNVFJBRJLPO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001741 organic sulfur group Chemical group 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 2
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- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 abstract 1
- -1 alcohol amine Chemical class 0.000 abstract 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract 1
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- GWZOLWLJEJRQMZ-UHFFFAOYSA-N [S].S Chemical compound [S].S GWZOLWLJEJRQMZ-UHFFFAOYSA-N 0.000 description 9
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 239000000446 fuel Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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Abstract
The invention provides a desulfuration method of environmental-friendly liquefied petroleum gas. In the invention, after alcohol amine elution is carried out on the liquefied petroleum gas to remove the sulfureted hydrogen, the membrane separation technique is adopted for desulfuration in the complete absence of alkali, desulfurating agent or catalyst; The membrane separator adopts a plate-and-frame membrane separator and/or a spiral-wound membrane separator, the membrane material is the composite membrane composed of polyvinylidene fluoride basal membrane and telechelic hydroxyl polybutadiene-acrylonitrile membrane. The invention is characterized by high efficiency, environmental protection, easy operation and low operating cost and the like.
Description
Technical field
The present invention relates to a kind of desulfuration method of environmental-friendly liquefied petroleum gas.More specifically, the present invention relates to a kind of liquefied petroleum gas process hydramine wash-out except after hydrogen sulfide, adopt membrane separation technique to take off the environment-friendly type sulfur method of inorganic sulfur and organic sulfur.
Background technology
Liquefied petroleum gas is the product of petroleum refining process, is the important source material of petrochemical industry, domestic fuel.But the impurity such as the sulfide that contains in liquefied petroleum gas (as hydrogen sulfide, mercaptan) have brought great harm to following process utilization and the environment of liquefied petroleum gas.So LPG Desulfurization cleans production for liquefied petroleum gas and utilization has very important meaning; And the sulfur content height can make equipment corrosion, and this is also one of major reason of LPG Desulfurization.
Also there is regulation various countries for the sulfur content of liquefied petroleum gas.Adopt the total sulfur of standard GB11174-1997 " liquefied petroleum gas " regulation to limit the quantity of as China and be 343mg/m
3, GB9052.1-1988 " oil gas field liquefied petroleum gas " regulation total sulfur limit the quantity of and be 140-185mg/m
3What iso standard required is to be not more than 50mg/m
3, China's standard surpasses more than 3 times of iso standard requirement.The standard of the European countries such as Britain, Poland, Holland, Bulgaria is limited the quantity of generally to the total sulfur of civilian petroleum gas fuel, and requirement is 50-120mg/m
3, the standard of the U.S. is tighter, only has 22.9mg/m
3
Liquefied petroleum gas is mainly used in the heating of cooking of domestic fuel such as family, and as too high in sulfur content all can have severe contamination to family and urban air.Along with the raising of china's overall national strength, also can improve for the requirement of environmental protection aspect thereupon.
The sulfide that contains in liquefied petroleum gas comprises inorganic sulfur (hydrogen sulfide) and organic sulfur, and inorganic sulphide can be removed by the method that hydramine is washed, remove precision and can reach several ppm, then can hydrogen sulfide stripping is clean by making with extra care.Removing of organic sulfur compound is more difficult, and in petroleum gas sweetening technique, Merox technique is the technological process of generally adopting, after developed again tunica fibrosa doctor process and solid alkaline-free sweetening technique.
Merox technique and employing tunica fibrosa technique are all to adopt the method for caustic wash desulfuration alcohol, this class adopt the technique of caustic wash desulfuration alcohol all exist removal of mercaptans not exclusively, produce alkaline residue and process the alkaline residue secondary pollution, through after Merox liquid-liquid extraction desulfurization alcohol PROCESS FOR TREATMENT, removal of mercaptans in liquefied gas is converted into disulphide, although variation has occured the form of sulphur, the liquefied petroleum gas total sulfur does not change and for guaranteeing that desulfurization precision adopts suitable air speed to affect the problems such as treating capacity.Although adopt the tunica fibrosa desulfurization that the utilization rate of alkali is improved, but fundamentally do not solve the secondary pollution that alkaline residue brings and the drawback such as equipment is huge, heavy, operating cost is high.
Solid alkaline-free sweetening process using solid desulfurating agent and catalyst removal mercaptan although avoided process with the harm that processing of alkali and alkaline residue etc. causes, also exist equipment huge and frequently change agent, the more high drawback of production cost.
In sum, develop a kind of caustic alkali that do not use, and can remove the liquefied petroleum gas total sulfur, reduce energy consumption, sulfur removal technology simple to operate and effectively protection of the environment is imperative.
Chinese patent CN 101077984A discloses a kind of method of liquefied petroleum gas deep desulfuration, relate to a kind of under without the caustic alkali condition method of deep removal liquefied petroleum gas medium sulphide content, hydrogen sulfide is removed in the agent of liquefied petroleum gas process carbonyl sulfide hydrolysis, under the condition of certain oxygen or hydrogen peroxide existence, liquefied petroleum gas contacts with mercaptan-eliminating catalyst, make mercaptan oxidation become disulphide, liquefied petroleum gas is sent into and is removed disulphide in rectifying column.
Chinese patent CN 1072157A discloses a kind of method of refining catalytic liquefied petroleum gas, by complement lysis oxygen, mercaptan oxidation is become disulphide.
Chinese patent CN 1418937A discloses a kind of new method of industrialized refining liquefied petrolium gas (LPG).Under complete alkali-free condition, liquefied petroleum gas after processing through hydramine, carry out successively smart desulfurization and transform mercaptan by desulfurizing agent and the catalyst that is arranged in fixed bed reactors, during the essence desulfurization, the product of the hydrogen sulfide in liquefied petroleum gas and iron calcium oxide or the reaction of hydrated iron calcium oxide is attached on desulfurizing agent, when transforming mercaptan, in mercaptan in liquefied petroleum gas and liquefied petroleum gas, residual micro-air reacts under the catalytic action of catalyst and generates disulphide, and the disulphide that generates flows out fixed bed reactors with liquefied petroleum gas; Liquefied petroleum gas after conversion mercaptan obtains the liquefied petroleum gas highly finished product by rectification process; Further rectifying can obtain the disulphide product of high value.
Chinese patent CN 1687327A discloses a kind of method that alkyl sulfhydrate contained in liquefied petroleum gas is oxidized to disulphide.
Chinese patent CN 1347966A discloses a kind of new method that liquefied petroleum gas or natural gas are made with extra care.Hydrogen sulfide and thio-alcohol heteroatomic compound remove liquefied petroleum gas/natural gas under complete alkali-free condition in, and produce simultaneously the method for the thioether product of high value.
At present, also do not have in prior art a kind of efficient, easy and simple to handle, cost is low, the LPG Desulfurization method of environmental protection.
Summary of the invention
Main purpose of the present invention is to overcome defective of the prior art, provides a kind of efficient, environmental protection, simple process, cost the low method that removes inorganic sulfur and organic sulfur in liquefied petroleum gas.
The present invention adopts film and film device technology after liquefied petroleum gas removes most hydrogen sulfide through the hydramine wash-out, liquefied petroleum gas is removed inorganic sulfur and organic sulfur.
The present invention utilizes the dissolving diffusivity of film, makes the correlation molecule in the material of upstream at first be dissolved in film, then diffuses through film, at last desorb in the material of downstream.
Use composite membrane to the microcomponent in mixed material separate be the variable concentrations that utilizes the film both sides, dividing potential drop as motive force, film to the different infiltration coefficients of microcomponent to reach the purpose of separation.Because permeability is determined by solubility and diffusion coefficient, so the membrane material of selecting to be fit to the solubility of sulfide and the diffusion coefficient effective sulfide in the parting liquid liquefied oil gas reaches the purpose of parting liquid liquefied oil gas medium sulphide content.Contain few sulphur or without a large amount of liquefied petroleum gas of sulphur, isolate in the per-meate side (6) of film device the liquefied petroleum gas that is rich in sulfide thereby isolate in the side of damming (5) of film device.
In film device of the present invention, the membrane material of diaphragm is preferably compound organic separation membrane, most preferably the composite membrane of Kynoar basement membrane and poly-end hydroxy butadiene-acrylonitril membrane composition.Preferred Fig. 2 of film device used, plate and frame film device and/or rolled film device shown in Figure 3.
The film device that the present invention adopts is that the principle of utilizing above-mentioned membrane material to separate microcomponent is carried out work.In plate and frame film device, the high flow rate raw material enters plate and frame film device by material inlet (1), raw material stops in film (4) the surface short time and completes separation process, obtain being rich in the material of microcomponent in per-meate side (3), the material after being made with extra care from the refining material outlet (2) of the side of damming; The rolled film device is compared with plate and frame film device, its have the operation pressure drop large, raw material flow rate is slow, the characteristics such as good separating effect, raw material is crossed cylindric film device from raw material feed side (1) along the axial flow that is parallel to central tube, complete separation process on film (5) surface, and isolated penetrant radially flows to per-meate side collecting pipe (3), obtain being rich in the material of microcomponent at permeant outlet (2), the material after the side discharging opening (4) that dams is made with extra care.
preferred version provided by the invention is: process hydramine wash-out is except the liquefied petroleum gas after hydrogen sulfide, enter surge tank (2) from material inlet (1), by feedstock pump (3), be 0.1-2.0MPa at pressure, temperature is under 0-100 ℃ of condition, by being used for the film device (4) of organic sulfide removal and a small amount of hydrogen sulfide, isolate and contain few sulphur or without a large amount of liquefied petroleum gas of sulphur in the film device side (5) of damming, liquefied petroleum gas exports (8) by liquefied petroleum gas and enters refining liquefied petrolium gas (LPG) collecting tank (9), obtain refining liquefied petrolium gas (LPG), isolate the liquefied petroleum gas that is rich in sulfide and the material of a small amount of liquefied petroleum gas in film device per-meate side (6), be delivered to rich sulphur liquefied petroleum gas collecting tank (10) through product pump (7).
Another preferred version of the present invention is that in the liquefied petroleum gas after hydramine is washed, the concentration of hydrogen sulfide is less than or equal to 1000ppm, is more preferably less than or equals 100ppm; Organic sulfur concentration is more than or equal to 5ppm, more preferably greater than or equal 50ppm.
Method of the present invention can make liquefied petroleum gas isolate more than or equal to 99% low-sulfur or without the refining liquefied petrolium gas (LPG) of sulphur in the film device side of damming by the film device, isolates in film device per-meate side to be less than or equal to 1% the liquefied petroleum gas that is rich in sulfide.
The present invention adopts the membrane separation technique desulfurization to liquefied petroleum gas under fully alkali-free, desulfurizing agent and catalyst condition, because of in the film device without solid formulation, therefore not affected by the air speed factor, feed throughput is large, flow velocity is high.
After operation a period of time, membrane flux is changed diaphragm during less than design load 2/3, changes 50% diaphragm at every turn.
The present invention has carried out larger change to existing LPG Desulfurization technique, can replace existing Merox technique and solid alkaline-free sweetening technique.
Compared with prior art, the present invention has following technical advantage: (1) the present invention can carry out refining desulfurization to the high raw liquefied petroleum gas of organic sulfur content; (2) membrane separation process used in the present invention and traditional Merox technique and the Merox technique that increases tunica fibrosa are compared with solid alkaline-free sweetening technique, and cost is low and desulfuration efficiency is high; (3) do not use alkali lye in process, do not produce alkaline residue, do not produce environmental pollution; (4) do not use the containers such as Large Towers, tank, do not relate to the dress agent and unload the problems such as agent and useless agent processing, equipment is simple, convenient, and operating cost is low; (5) the gained liquefied petroleum gas that is rich in sulfide can be used as refinery, the unstripped gas of photoelectric decomposition sulphur processed and hydrogen particularly, but also Re-isolation goes out high-purity mercaptan, and mercaptan conversion product disulphide is recycled; (6) there is not the factor that operation is controlled by air speed in the present invention, has solved the bottleneck for the treatment of capacity.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
The 1 material inlet 2 surge tank 3 feedstock pump 4 film device 5 film devices side of damming
6 film device per-meate side 7 product pump 8 liquefied petroleum gas outlets
The 9 rich sulphur liquefied petroleum gas of refining liquefied petrolium gas (LPG) collecting tank 10 collecting tanks
Fig. 2 is plate and frame film device structural representation
1 material inlet 2 refining material outlet 3 per-meate side 4 films of side that dam
Fig. 3 is rolled film device structural representation
1 raw material feed side 2 permeant outlet 3 per-meate side collecting pipes 4 side discharging opening 5 films that dam
The specific embodiment:
Embodiment 1
Raw material is sulfide hydrogen 39ppm, the 320ppm mercaptan sulfur, the catalytic liquefied petroleum gas of 51ppm cos sulphur, by feedstock pump in operating pressure 0.8 MPa (MPa), enter the film device under 30 ℃ of conditions of operating temperature, the Kynoar basement membrane of process plate and frame film device separates with the composite membrane of poly-end hydroxy butadiene-acrylonitril membrane composition, the side of holding back at the film device obtains 99.03% refining liquefied petrolium gas (LPG), hydrogen sulfide sulfur content 1ppm, mercaptan sulfur content 4ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.97% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 3928ppm, mercaptan sulfur content 32581ppm, cos sulphur 5155ppm.
Raw material is sulfide hydrogen 30ppm, the 2000ppm mercaptan sulfur, the coking liquefied petroleum gas of 30ppm3 cos sulphur, by feedstock pump in operating pressure 0.8 MPa (MPa), enter the film device under 30 ℃ of conditions of operating temperature, the Kynoar basement membrane of process plate and frame film device separates with the composite membrane of poly-end hydroxy butadiene-acrylonitril membrane composition, the side of holding back at the film device obtains 99.17% refining liquefied petrolium gas (LPG), hydrogen sulfide content 1ppm, mercaptan sulfur content 5ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.83% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 3542ppm, mercaptan sulfur content 240366ppm, cos sulphur 3483ppm.
Raw material is for containing 40ppm hydrogen sulfide sulphur, mercaptan sulfur 300ppm, the catalytic liquefied petroleum gas of cos sulphur 30ppm, by feedstock pump in operating pressure 0.8 MPa (MPa), enter the film device under 30 ℃ of conditions of operating temperature, separating of the composite membrane that forms through the Kynoar basement membrane of rolled film device and poly-end hydroxy butadiene-acrylonitril membrane, the side of holding back at the film device obtains 99.09% refining liquefied petrolium gas (LPG), hydrogen sulfide sulfur content 1ppm, mercaptan sulfur content 6ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.91% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 4308ppm, mercaptan sulfur content 32313ppm, cos sulphur 3220ppm.
Embodiment 4
Raw material is for containing 35ppm hydrogen sulfide sulphur, mercaptan sulfur 2320ppm, the coking liquefied petroleum gas of cos sulphur 47ppm, by feedstock pump in operating pressure 0.8 MPa (MPa), enter the film device under 30 ℃ of conditions of operating temperature, the Kynoar basement membrane of process plate and frame film device separates with the composite membrane of poly-end hydroxy butadiene-acrylonitril membrane composition, the side of holding back at the film device obtains 99.05% refining liquefied petrolium gas (LPG), hydrogen sulfide sulfur content 1ppm, mercaptan sulfur content 6ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.95% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 3621ppm, mercaptan sulfur content 243584ppm, cos sulphur 4853ppm.
Raw material is for containing 51ppm hydrogen sulfide sulphur, mercaptan sulfur 310ppm, the catalytic liquefied petroleum gas of cos sulphur 40ppm, by feedstock pump in operating pressure 1.4 MPas (MPa), enter the film device under 30 ℃ of conditions of operating temperature, the Kynoar basement membrane of process plate and frame film device separates with the composite membrane of poly-end hydroxy butadiene-acrylonitril membrane composition, the side of holding back at the film device obtains 99.21% refining liquefied petrolium gas (LPG), hydrogen sulfide sulfur content 0ppm, mercaptan sulfur content 3ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.79% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 6556ppm, mercaptan sulfur content 38864ppm, cos sulphur 5000ppm.
Embodiment 6
Raw material is for containing 40ppm hydrogen sulfide sulphur, mercaptan sulfur 350ppm, the catalytic liquefied petroleum gas of cos sulphur 30ppm, by feedstock pump in operating pressure 1.4 MPas (MPa), enter the film device under 30 ℃ of conditions of operating temperature, separating of the composite membrane that forms through the Kynoar basement membrane of rolled film device and poly-end hydroxy butadiene-acrylonitril membrane, the side of holding back at the film device obtains 99.15% refining liquefied petrolium gas (LPG), hydrogen sulfide sulfur content 0ppm, mercaptan sulfur content 4ppm, cos sulphur 1ppm; Per-meate side at the film device obtains 0.85% the liquefied petroleum gas that is rich in sulfide, hydrogen sulfide content 4671ppm, mercaptan sulfur content 40710ppm, cos sulphur 3471ppm.
The above embodiment is only most preferred embodiment of the present invention; for the purpose of description, in order to limit the present invention, within the spirit and principles in the present invention not all; any modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (6)
1. a desulfuration method of environmental-friendly liquefied petroleum gas, is characterized in that, will remove the liquefied petroleum gas of hydrogen sulfide through the hydramine wash-out, is that 0.8~1.4MPa, temperature are under 30~100 ℃ at pressure, obtaining refining liquefied petrolium gas (LPG) by being used for the film device of desulfurization, separating;
Described film device is plate and frame film device and/or rolled film device;
The diaphragm material of described film device is the composite membrane that Kynoar basement membrane and poly-end hydroxy butadiene-acrylonitril membrane form.
2. the described sulfur method of claim according to claim 1, is characterized in that comprising the steps:
(a) through the liquefied petroleum gas of hydramine wash-out except hydrogen sulfide, be that 0.8~1.4MPa, temperature are under 30~100 ℃ at pressure, by being used for the film device of desulfurization;
(b) separate and to obtain refining liquefied petrolium gas (LPG) in the film device side of damming, the refining liquefied petrolium gas (LPG) that obtains enters the refining liquefied petrolium gas (LPG) collecting tank;
(c) isolate the liquefied petroleum gas that is rich in sulfide and the material of liquefied petroleum gas in film device per-meate side, be delivered to rich sulphur liquefied petroleum gas collecting tank through product pump.
3. sulfur method according to claim 2 is characterized in that: described in step (a), through the liquefied petroleum gas of hydramine wash-out except hydrogen sulfide, the concentration of its hydrogen sulfide is less than or equal to 1000ppm; Organic sulfur concentration is more than or equal to 5ppm.
4. sulfur method according to claim 3 is characterized in that: described in step (a), through the liquefied petroleum gas of hydramine wash-out except hydrogen sulfide, the concentration of its hydrogen sulfide is less than or equal to 100ppm; Organic sulfur concentration is more than or equal to 50ppm.
5. sulfur method according to claim 4 is characterized in that: at the film device separable refining liquefied petrolium gas (LPG) that goes out more than or equal to 99% of side that dams.
6. sulfur method according to claim 5, is characterized in that, the membrane flux of film device is changed diaphragm during less than design load 2/3, changes 50% diaphragm at every turn.
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CN1895761A (en) * | 2006-06-15 | 2007-01-17 | 清华大学 | Organic steam-separated blend composite film and its production |
CN101186841A (en) * | 2001-02-16 | 2008-05-28 | 格雷斯公司 | Membrane separation method for sulfur reduction |
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US6649061B2 (en) * | 2000-12-28 | 2003-11-18 | Exxonmobil Research And Engineering Company | Membrane process for separating sulfur compounds from FCC light naphtha |
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