CN104371782A - Liquefied petroleum gas alkali solution desulfurization method and device - Google Patents
Liquefied petroleum gas alkali solution desulfurization method and device Download PDFInfo
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- CN104371782A CN104371782A CN201310352347.8A CN201310352347A CN104371782A CN 104371782 A CN104371782 A CN 104371782A CN 201310352347 A CN201310352347 A CN 201310352347A CN 104371782 A CN104371782 A CN 104371782A
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Abstract
The invention provides a liquefied petroleum gas alkali solution desulfurization method and device. The provided alkali solution desulfurization method comprises the following steps: (1) contacting/mixing an alkali solution with a deoxidizer to remove the oxidizing substances in the alkali solution, wherein the deoxidizer is a reducing substance that can be in oxidation-reduction reaction with the oxidizing substances but cannot be reacted with the alkali solution; (2) contacting the alkali solution without oxidizing substance with liquefied petroleum gas to carry out desulfurization reactions, and collecting the liquefied petroleum gas product. The provided alkali solution desulfurization method and device can avoid or reduce the generation of disulfides or polysulfide, and prominently increases the desulfurization efficiency of the alkali solution desulfurization technology. The sulfur content of the liquefied petroleum gas is greatly reduced after desulfurization.
Description
Technical field
The present invention relates to the sulfur method of liquefied petroleum gas (LPG), particularly a kind of alkali lye sulfur method of liquefied petroleum gas (LPG).
Background technology
As everyone knows, MTBE(methyl tertiary butyl ether) be non-hydrocarbons high-octane rating blending component maximum in China's gasoline, can quality of gasoline be significantly improved.But under existing working condition, obviously containing sulfide in the MTBE of output, generally sulphur content reaches 60 ~ 300mg/kg, and the sulphur content of the MTBE of part manufacturer production is sometimes especially up to 2000mg/kg.
MTBE can be synthesized in acid condition by iso-butylene and methyl alcohol, industrial direct use containing iso-butylene liquefied petroleum gas (LPG) in as raw material, the production cost of MTBE is significantly reduced.But international standard requires not become to the sulphur content of civil LPG for many years, and its standard is for being not more than 343mg/m always
3(about corresponding to 150mg/kg), and be significantly improve for the requirement of content of sulfur in gasoline, the sulphur content starting the state II gasoline performed for such as 2005 requires to be not more than 500mg/kg, requires that sulphur content is not more than 150mg/kg during 2008 years state of enforcement III.State Environmental Protection Administration explicitly calls for, require during nationwide state of enforcement IV in 2014 that sulphur content is not more than 50mg/kg, subsequently state of enforcement V sulphur content is not more than the standard of 10mg/kg, and urban is if Shanghai etc. is at state of enforcement IV, and Beijing state of enforcement V gasoline standard.
Research finds, in the building-up process of MTBE, partial vulcanization thing in liquefied petroleum gas (LPG) is converted into the sulfide in MTBE, but because liquefied petroleum gas (LPG) sulphur content requires substantially constant, the sulfur removal technology of the liquefied petroleum gas (LPG) of factory, operational condition is caused to change little, make the liquefied petroleum gas (LPG) sulphur content of production qualified, but the sulphur content of the MTBE produced by liquefied petroleum gas (LPG) is generally 2 ~ 3 times of sulphur content in liquefied petroleum gas (LPG), as sulphur content 200mg/m
3the liquefied petroleum gas (LPG) of (about corresponding to 80mg/kg) is after gas divides, and the sulphur content in C4 is about 400mg/m
3(about corresponding to 180mg/kg), the sulphur content in the MTBE of production is about 400mg/kg.
Due to the quick upgrading of quality of gasoline, requirement for sulphur content is more and more stricter, the sulphur content problem of MTBE is become increasingly conspicuous, if significantly do not reduce the sulphur content in MTBE, following MTBE can cannot call in gasoline because sulphur content is too high, and this will cause existing MTBE production equipment to use, or significantly raise the production cost of domestic gasoline, the direct production and supply affecting gasoline, also has influence on the Appropriate application of the resource of refinery's liquefied petroleum gas (LPG).
On the other hand, although do not significantly improve for the requirement of civil LPG sulphur content, in some fields, the requirement for the sulphur content of liquefied petroleum gas (LPG) is also more and more higher.Such as both at home and abroad the be not more than 200mg/kg of the requirement of sulphur content from the nineties in last century is dropped to and present be not more than 10mg/kg in Vehicular liquefied petroleum gas standard, during as industrial chemicals or synthetic oil raw material, sulphur content for liquefied petroleum gas (LPG) also has very strict requirement, sometimes even requires to reach without sulphur (below 0.5mg/kg).
Having a kind of method of conventional desulfurization, is the hybrid C 4 re-distillation again after being divided by gas, and be cut into light C4 and heavy C4, wherein light C4 iso-butylene content is higher, and sulphur content is lower, and as etherificate or raw material for alkylation, the sulphur content of the MTBE obtained after etherificate is also lower; Heavy C4 is then mainly as the blending stock of liquefied petroleum gas (LPG), and the most of sulfide in C4 focuses at this cut.The shortcoming one of this technique is that redistilled energy consumption is higher, and two is that cause being difficult to be separated thoroughly, the sulphur content of the MTBE that result obtains also is difficult to take off below 10mg/kg because the light C4 such as C4 medium sulphide content boiling point and iso-butylene is more or less the same.
CN101077984 describes a kind of method of liquefied petroleum gas (LPG) deep desulfuration, liquefied petroleum gas (LPG) after alcohol amine removal hydrogen sulfide, make carbonyl sulfide hydrolysis by hydrolyst and be desulfurized agent to absorb, realize removing of inorganic sulfur in liquefied gas, mercaptan in liquefied gas is converted into disulphide by the oxygen being decomposed generation by hydrogen peroxide under catalytic condition under mercaptan-eliminating catalyst effect, by rectifying, obtain the liquefied petroleum gas (LPG) of low-sulfur.
CN1687327 provides a kind of method alkyl sulfhydrate contained in liquefied petroleum gas being converted into disulphide, air or oxygen is pumped into removing being in the liquefied petroleum gas (LPG) of flow state after hydrogen sulfide treatment through hydramine method, in flowing, air or oxygen dissolution are in liquefied petroleum gas (LPG), when the liquefied petroleum gas (LPG) that this is dissolved with air or oxygen by be arranged in fixed-bed reactor there is the beds of mercaptan conversion catalyst performance time, under the effect of catalyzer, alkyl sulfhydrate contained in liquefied petroleum gas is oxidized to disulphide by the oxygen in liquefied petroleum gas (LPG).
CN1702157 disclose oily in the method for desulfuration purification catalytic liquefied petroleum gas, catalytic liquefied petroleum gas after alcohol amine removal of H2S process is hydrolyzed by hydrolytic catalyst of carbonyl sulfur bed and is removed the hydrogen sulfide of generation after carbonylsulfide process by sorbent material by the method, tertbutyl peroxide is added again in catalytic liquefied petroleum gas, make in liquefied petroleum gas (LPG), to obtain mercaptan oxidation and become disulphide, if rectifying further, can obtain the liquefied petroleum gas (LPG) of low sulfur content.
These methods, to a certain extent can inorganic sulfur in effective elimination liquefied petroleum gas (LPG) and organosulfur, or by organic sulfur conversion.Common feature is all for liquefied petroleum gas (LPG) itself, adopts conventional desulfuration processing method, all mercaptan has been carried out simple oxidation process.But in fact use superoxide to have very large potential safety hazard as the source of oxygenant or oxygen in liquefied petroleum gas (LPG) factory, and be distillate liquefied oil gas again after disulphide by the mercaptan oxidation in liquefied petroleum gas (LPG), liquefied petroleum gas (LPG) is needed all again to gasify, ensure the thorough separation of the disulphide at the bottom of tower, the energy consumption of operation is very high, and again enters the problem in the liquefied petroleum gas (LPG) steamed after also having disulphide or polysulfide decomposed.
Existing LPG Desulfurization technique encounters bottleneck: sulphur content is reduced to a certain degree, no matter adopt great cost, sulphur content no longer reduce or improvement amplitude very little, but resource is at double consumed in vain: add device, multiplex auxiliary agent, consume a large amount of alkali lye and amine liquid, significantly increase the environmental protection treatment pressure of alkaline sewage simultaneously.
Find under study for action, when dissolved oxygen in alkali lye or micro amount of oxygen voltinism impurity make liquefied petroleum carry out alkali lye desulfurization, part mercaptan can be oxidized to disulphide or polysulfide, these disulphide or polysulfide are fat-soluble cpds, by permanent " resident " in liquefied petroleum gas (LPG), be difficult to remove; When these are dissolved in sulfide in liquefied petroleum gas (LPG) when running into strongly acidic cation-exchange, part can generate high boiling thioether with isobutene reaction, part residues in MTBE as high boiling polysulfide, almost becomes whole sources of MTBE sulphur content.
Summary of the invention
The invention provides a kind of alkali lye sulfur method and device of liquefied petroleum gas (LPG).
Alkali lye sulfur method of the present invention comprises: alkali lye contacts with reductor or mixes the oxidizing substance removed in alkali lye by (1), and described reductor is the reducing substances that can not react with described oxidizing substance generation redox reaction and with described alkali lye; (2) alkali lye removing oxidizing substance is contacted with liquefied petroleum gas (LPG) carry out alkali lye desulphurization reaction, collect liquefied petroleum gas product.
Described alkali lye is the aqueous solution of alkali metal hydroxide, and described alkali metal hydroxide accounts for 5 ~ 30% of aqueous solution total mass, preferably 8 ~ 25%, most preferably 12 ~ 20%.The preferred aqueous sodium hydroxide solution of described alkali lye and/or potassium hydroxide aqueous solution, most preferably aqueous sodium hydroxide solution.
Preferably metal phthalocyanine catalyst is added and/or metal gathers phthalocyanine catalyst, such as Cobalt Phthalocyanine, sulfonated phthalocyanine cobalt, poly-phthalocyanine cobalt catalyst, most preferably sulfonation's phthalocyanin metalic catalyzer in described alkali lye.The add-on that described metal phthalocyanine catalyst and/or metal gather phthalocyanine catalyst is preferably 0.1 ~ 1000mg/kg of alkali lye, most preferably 1 ~ 500mg/kg.
Described oxidizing substance is dissolved oxygen in alkali lye, gas phase oxygen and/or the oxide compound that generates in continuous alkali lye sulfur removal technology.
In continuous print alkali lye sulfur removal technology, because alkali lye constantly can contact extraneous oxygen, oxygen can react with alkali lye and the hydrocarbons carried secretly thereof, sulfide oxide compounds such as generating peroxy acid, sulfurous acid,-sulfinic acid, and after contacting with liquefied petroleum gas (LPG) with the alkali lye of oxide compound containing dissolved oxygen, gas phase oxygen, can be disulphide or polysulfide by the mercaptan oxidation in liquefied petroleum gas (LPG), these disulphide or polysulfide are fat-soluble cpds, by permanent " resident " in liquefied petroleum gas (LPG), be difficult to be removed.Therefore only remove the oxidizing substance in alkali lye, the desulfuration efficiency of alkali lye sulfur removal technology could be improved, thoroughly remove the sulfide in liquefied petroleum gas (LPG).
Described reductor can select in gaseous state reductor, liquid deoxidizer and solid-state reductor one or more, preferably can be dissolved in the liquid deoxidizer of alkali lye, solid-state reductor and/or be insoluble to the solid-state reductor of alkali lye.The method that alkali lye and the liquid state that can be dissolved in wherein and/or solid-state reductor can be adopted to mix mutually removes oxidizing substance wherein, and the method that alkali lye and solid-state reductor insoluble with it also can be adopted to contact removes oxidizing substance wherein.
The preferred H of described gaseous state reductor
2, CO, one or more in hydrazine.
Described liquid state or solid-state reductor can select in ketoxime class, aldoxime class, hydrazine class, sulphite, reducing metal and reductibility resin one or more, such as can select DMKO (acetoxime, DMKO) one or more, in Diacetylmonoxime, ethylidenehydroxylamine, hydrazine hydrate, S-WAT and vitamin-E, the preferred reducing metal bits of described reducing metal and/or sponge state reducing metal, such as can select steel cuttings, sponge iron, one or more in the preferred hydroquinone type of described reductibility resin, sulfydryl class, pyridines and ferrocene resinoid.
Described can be dissolved in the liquid deoxidizer of alkali lye, the preferred ketoxime class of solid-state reductor, aldoxime class, hydrazine class and sulphite one or more, described in be insoluble to the preferred reducing metal of solid-state reductor and/or the reductibility resin of alkali lye.
The preferred add-on of described reductor is 0.1 ~ 200mg/kg of alkali lye, most preferably 1 ~ 80mg/kg.
The content of described oxidizing substance in alkali lye is generally more than 10mg/L; Remove after described oxidizing substance through the inventive method, in alkali lye, the content of oxidizing substance can be down to below 0.1mg/L.
Main alkane, aromatic hydrocarbons, alkene or their mixture containing C3 ~ C20 in described liquefied petroleum gas (LPG).Sulfide in liquefied petroleum gas (LPG) is mainly H
2s, mercaptan, carbonylsulfide.
The processing condition removing the alkali lye of oxidizing substance and liquefied petroleum gas (LPG) generation desulphurization reaction are as follows:
The volume ratio of described alkali lye and liquefied petroleum gas (LPG) is 1:1 ~ 1:50, preferred 1:1 ~ 1:20, most preferably 1:2 ~ 1:10.
The Contact Temperature of described alkali lye and liquefied petroleum gas (LPG) is 10 ~ 80 DEG C, preferably 20 ~ 60 DEG C, most preferably 30 ~ 50 DEG C.
Described desulphurization reaction preferably carries out at reactor.
When desulphurization reaction carries out in the reactor, volume space velocity preferably 0.1 ~ 12h during the liquid of described liquefied petroleum gas (LPG)
-1, most preferably 0.2 ~ 10h
-1.
After described alkali lye and liquefied petroleum gas (LPG) generation desulphurization reaction, reuse after can regenerating.Oxidized regenerating method can be selected to make alkali liquid regeneration, and the method is in alkali lye, inject oxygen or air, and then back suction carries the sulfide or employing sedimentation method separate sulfur compound and alkali lye that generate in oxidizing reaction, thus obtains the alkali lye without sulphur, makes alkali liquid regeneration.
Alkali lye contacts with reductor or mixes the oxidizing substance removed in alkali lye by alkali lye sulfur method of the present invention, then contact with liquefied petroleum gas (LPG) and carry out alkali lye desulphurization reaction, collect liquefied petroleum gas product, reuse after alkali liquid regeneration, the continuous processing of alkali lye desulfurization can be realized like this.
The invention provides a kind of alkali lye desulfurizer of liquefied petroleum gas (LPG), comprise alkali lye desulfurization unit 301, alkali liquid regeneration unit 302, it is characterized in that, the alkali lye return line 43 between described alkali lye desulfurization unit 301 and alkali liquid regeneration unit 302 is provided with the intake pipeline 48 of reductor intake pipeline 45 or reductor and alkali lye mixture.Described alkali liquid regeneration unit 302 preferred bases liquid oxidation regeneration unit.
Alkali lye desulfurizer schematic diagram of the present invention can see Fig. 1,2.
As shown in Figure 1, 2, liquefied petroleum gas (LPG) intake pipeline 41 is connected with alkali lye desulfurization unit 301, alkali lye desulfurization unit 301 is connected with alkali liquid regeneration unit 302 through alkali lye intake pipeline 42, alkali liquid regeneration unit 302 returns alkali lye desulfurization unit through alkali lye return line 43, alkali lye return line 43 between alkali lye desulfurization unit 301 and alkali liquid regeneration unit 302 is provided with the intake pipeline 48 of reductor intake pipeline 45, alkali lye intake pipeline 46 or reductor and alkali lye mixture, the liquefied petroleum gas (LPG) after alkali lye desulfurization is discharged through its export pipeline 44 and is collected product.
The preferred alkali lye desulfurizer of the present invention comprises alkali lye desulfurization unit 301, alkali liquid regeneration unit 302, it is characterized in that, alkali lye return line 43 between described alkali lye desulfurization unit 301 and alkali liquid regeneration unit 302 is provided with alkali lye deacidification unit 303, described alkali lye deacidification unit 303 is provided with the intake pipeline 48 of reductor intake pipeline 45 or reductor and alkali lye mixture or reductor stationary installation a is set in alkali lye deacidification unit 303 inside.The preferred reductor fixed bed of described reductor stationary installation a, preferably places the solid-state reductor being insoluble to alkali lye, such as reducing metal and/or reductibility resin in described reductor stationary installation a.
The present invention's preferred alkali lye desulfurizer schematic diagram can see Fig. 3,4.
As Fig. 3, shown in 4, liquefied petroleum gas (LPG) intake pipeline 41 is connected with alkali lye desulfurization unit 301, alkali lye desulfurization unit 301 is connected with alkali liquid regeneration unit 302 through alkali lye intake pipeline 42, alkali liquid regeneration unit 302 returns alkali lye desulfurization unit through alkali lye return line 43, alkali lye return line 43 between described alkali lye desulfurization unit 301 and alkali liquid regeneration unit 302 is connected with alkali lye deacidification unit 303, described alkali lye deacidification unit 303 arranges reductor intake pipeline 45, the intake pipeline 48 of alkali lye intake pipeline 46 or reductor and alkali lye mixture, or reductor stationary installation a is set in alkali lye deacidification unit 303 inside, liquefied petroleum gas (LPG) after alkali lye desulfurization is discharged through its export pipeline 44 and is collected product.
The generation of disulphide, polysulfide can be avoided or reduce to alkali lye sulfur method of the present invention and device, and significantly improve the desulfuration efficiency of alkali lye sulfur removal technology, the sulphur content after desulfurization in liquefied petroleum gas (LPG) significantly reduces.
Accompanying drawing explanation
Fig. 1 is alkali lye desulfurizer schematic diagram of the present invention.
Fig. 2 is alkali lye desulfurizer schematic diagram of the present invention.
Fig. 3 is the present invention's preferred alkali lye desulfurizer schematic diagram.
Fig. 4 is the present invention's preferred alkali lye desulfurizer schematic diagram.
Embodiment
Unless stated otherwise, the per-cent below mentioned is mass percent.
Before desulfurization, after desulfurization, the sulphur content of liquefied petroleum gas (LPG) adopts SH/T0222 method to measure, and sulfur speciation distribution adopts GC-SCD method to measure.
In the present invention, raw materials used source is as follows:
Catalytic liquefied petroleum gas, take from the stable liquefied gas of China Petrochemical Corp. subordinate refinery MIP technique, this liquefied petroleum gas (LPG) is stripped of hydrogen sulfide through hydramine composite desulfurizing agent, and sulfide composition is in table 1;
The sulfide composition of table 1 catalytic liquefied petroleum gas
| Various sulfide content | Catalytic liquefied petroleum gas |
| Sulphur content/% | 0.0660 |
| Hydrogen sulfide sulphur/% | 0.0005 |
| Carbonylsulfide/% | 0.0001 |
| Mercaptan sulfur/% | 0.0478 |
| Disulphide sulphur/% | 0.0131 |
| Polysulfide sulphur/% | 0.0012 |
Coking liquefied petroleum gas (LPG), takes from the stable liquefied gas of China Petrochemical Corp. subordinate refinery delay coking process after the process of hydramine composite desulfurizing agent; The sulfide composition of this liquefied gas is in table 2.
The sulfide composition of table 2 coking liquefied petroleum gas (LPG)
| Various sulfide content | Catalytic liquefied petroleum gas |
| Sulphur content/% | 0.4398 |
| Hydrogen sulfide sulphur/% | 0.0025 |
| Carbonylsulfide/% | 0.0018 |
| Mercaptan sulfur/% | 0.4122 |
| Disulphide sulphur/% | 0.0222 |
| Polysulfide sulphur/% | 0.0052 |
| Other Sulfur/% | 0.0013 |
Embodiment 1
Below in conjunction with Fig. 1, alkali lye sulfur method of the present invention and device are described.
Pending liquefied petroleum gas (LPG) is the stable catalytic liquefied petroleum gas taking from China Petrochemical Corp. subordinate refinery MIP technique through hydramine process.The alkali lye used is the sodium hydroxide solution of 15%.
Alkali lye injects from alkali lye intake pipeline 46, reductor adopts concentration to be the hydrazine hydrate solution of 45%, inject through reductor intake pipeline 45, the two enters alkali lye desulfurization unit 301 through alkali lye return line 43, above-mentioned catalytic liquefied petroleum gas injects alkali lye desulfurization unit 301 through liquefied petroleum gas (LPG) intake pipeline 41, with alkali lye, reductor contacts, carry out desulfurization test, the processing condition adopted are: Contact Temperature is 40 DEG C, the volume ratio of alkali lye and liquefied petroleum gas (LPG) is 1:3, the add-on of reductor is the 10mg/kg of alkali lye quality, during the liquid of catalytic liquefied petroleum gas, volume space velocity is 10h
-1.
Comparative example 1
Desulfurization test, with embodiment 1, does not just add reductor, but directly uses alkali lye to carry out desulfurization test to catalytic liquefied petroleum gas.
Raw materials used catalytic liquefied petroleum gas and after embodiment 1 and comparative example 1 desulfurization process the composition of liquefied petroleum gas (LPG) medium sulphide content in table 3.
The sulphur content of catalytic liquefied petroleum gas before and after table 3 desulfurization process
| Various sulfide content | Catalytic liquefied petroleum gas | Embodiment 1 | Comparative example 1 |
| Sulphur content/% | 0.0660 | 0.0157 | 0.0275 |
| Hydrogen sulfide sulphur/% | 0.0005 | 0.0000 | 0.0000 |
| Carbonylsulfide/% | 0.0001 | 0.0000 | 0.0000 |
| Mercaptan sulfur/% | 0.0478 | 0.0001 | 0.0001 |
| Disulphide sulphur/% | 0.0131 | 0.0134 | 0.0228 |
| Polysulfide sulphur/% | 0.0012 | 0.0012 | 0.0032 |
Embodiment 2
Below in conjunction with Fig. 2, alkali lye sulfur method of the present invention and device are described.
Pending liquefied petroleum gas (LPG) is through hydramine process, takes from the stable liquid liquefied oil gas of China Petrochemical Corp. subordinate refinery delay coking process.
The alkali lye used is the sodium hydroxide solution of 15%, and wherein sulfonated phthalocyanine cobalt contents is the 150mg/kg of alkali lye quality.Then in alkali lye, add the reductor hydrazine hydrate solution that concentration is 45%, its add-on is the 10mg/kg of alkali lye quality.
The mixture of alkali lye and reductor injects from the intake pipeline 48 of reductor and alkali lye mixture, alkali lye desulfurization unit 301 is entered through alkali lye return line 43, described alkali lye desulfurization unit 301 is packing tower, above-mentioned coking liquefied petroleum gas (LPG) injects alkali lye desulfurization unit 301 through liquefied petroleum gas (LPG) intake pipeline 41, with alkali lye, reductor contacts, carry out desulfurization test, the processing condition adopted are: counter current contact in packing tower, Contact Temperature is 42 DEG C, alkali lye, the mixture of reductor and the volume ratio of liquefied petroleum gas (LPG) are 1.5:1, during the liquid of coking liquefied petroleum gas (LPG), volume space velocity is 10h
-1.
Embodiment 3
Below in conjunction with Fig. 4, alkali lye sulfur method of the present invention and device are described.
Pending liquefied petroleum gas (LPG) is through hydramine process, takes from the stable liquid liquefied oil gas after China Petrochemical Corp. subordinate refinery delay coking process.
The alkali lye used is the sodium hydroxide solution of 15%, and wherein sulfonated phthalocyanine cobalt contents is the 150mg/kg of alkali lye quality.Then in alkali lye, add the DMKO solution that concentration is 50%, its add-on is the 10mg/kg of alkali lye quality.
Alkali lye injects from alkali lye intake pipeline 46, reductor employing concentration is the DMKO solution of 50%, inject through reductor intake pipeline 45, the two enters alkali lye deacidification unit 303 through alkali lye return line 43, process alkali lye being removed to oxidizing substance is completed in alkali lye deacidification unit 303, then alkali lye desulfurization unit 301 is entered, above-mentioned coking liquefied petroleum gas (LPG) injects alkali lye desulfurization unit 301 through liquefied petroleum gas (LPG) intake pipeline 41, with alkali lye, reductor contacts, carry out desulfurization test, the processing condition adopted are: counter current contact in packing tower, Contact Temperature is 42 DEG C, the volume ratio of alkali lye and liquefied petroleum gas (LPG) is 1.5:1, the add-on of reductor is the 10mg/kg of alkali lye quality, during the liquid of coking liquefied petroleum gas (LPG), volume space velocity is 8h
-1.
Comparative example 2
Desulfurization test, with embodiment 3, does not just add reductor in alkali lye, but directly uses alkali lye to carry out desulfurization test to coking liquefied petroleum gas (LPG).
Raw materials used coking liquefied petroleum gas (LPG) and after embodiment 2,3 and comparative example 2 desulfurization process the composition of liquefied petroleum gas (LPG) medium sulphide content in table 4.
The sulphur content of coking liquefied petroleum gas (LPG) before and after table 4 desulfurization process
| Various sulfide content | Coking liquefied petroleum gas (LPG) | Embodiment 2 | Embodiment 3 | Comparative example 2 |
| Sulphur content/% | 0.4398 | 0.0295 | 0.0290 | 0.0530 |
| Hydrogen sulfide sulphur/% | 0.0025 | 0.0000 | 0.0000 | 0.0000 |
| Carbonylsulfide/% | 0.0018 | 0.0000 | 0.0000 | 0.0000 |
| Mercaptan sulfur/% | 0.4122 | 0.0001 | 0.0002 | 0.0004 |
| Disulphide sulphur/% | 0.0222 | 0.0225 | 0.0220 | 0.0442 |
| Polysulfide sulphur/% | 0.0052 | 0.0055 | 0.0053 | 0.0072 |
| Other Sulfur/% | 0.0013 | 0.0015 | 0.0014 | 0.0010 |
From table 3,4, after adopting the alkali lye through removing oxidizing substance process to carry out desulphurization reaction, the mercaptan in liquefied petroleum gas (LPG) is substantially no longer converted into disulphide, and sweetening effectiveness greatly improves.
Claims (14)
1. the alkali lye sulfur method of a liquefied petroleum gas (LPG), comprise: alkali lye contacts with reductor or mixes the oxidizing substance removed in alkali lye by (1), described reductor is the reducing substances that can not react with described oxidizing substance generation redox reaction and with described alkali lye; (2) alkali lye removing oxidizing substance is contacted with liquefied petroleum gas (LPG) carry out alkali lye desulphurization reaction, collect liquefied petroleum gas product.
2. in accordance with the method for claim 1, it is characterized in that, described reductor is one or more in gaseous state reductor, liquid deoxidizer and solid-state reductor.
3. in accordance with the method for claim 2, it is characterized in that, described gaseous state reductor is H
2, CO or hydrazine.
4. in accordance with the method for claim 2, it is characterized in that, described liquid state or solid-state reductor are one or more in ketoxime class, aldoxime class, hydrazine class, sulphite, reducing metal and reductibility resin.
5. in accordance with the method for claim 2, it is characterized in that, described liquid state or solid-state reductor are one or more in DMKO, Diacetylmonoxime, ethylidenehydroxylamine, hydrazine hydrate, S-WAT and vitamin-E.
6. in accordance with the method for claim 4, it is characterized in that, described reductibility resin be selected from hydroquinone type, sulfydryl class, pyridines and ferrocene resinoid one or more.
7. in accordance with the method for claim 1, it is characterized in that, the add-on of described reductor is 0.1 ~ 200mg/kg of alkali lye.
8. in accordance with the method for claim 1, it is characterized in that, add metal phthalocyanine catalyst in described alkali lye and/or metal gathers phthalocyanine catalyst, the add-on that described metal phthalocyanine catalyst and/or metal gather phthalocyanine catalyst is 0.1 ~ 1000mg/kg of alkali lye.
9. in accordance with the method for claim 1, it is characterized in that, reuse after described alkali liquid regeneration.
10. according to the method one of claim 1-9 Suo Shu, it is characterized in that, the processing condition removing the alkali lye of oxidizing substance and liquefied petroleum gas (LPG) generation desulphurization reaction are as follows: the volume ratio of described alkali lye and liquefied petroleum gas (LPG) is 1:1 ~ 1:50, and the Contact Temperature of described alkali lye and liquefied petroleum gas (LPG) is 10 ~ 80 DEG C.
The alkali lye desulfurizer of 11. 1 kinds of liquefied petroleum gas (LPG), comprise alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), it is characterized in that, the alkali lye return line (43) between described alkali lye desulfurization unit (301) and alkali liquid regeneration unit (302) is provided with the intake pipeline (48) of reductor intake pipeline (45) or reductor and alkali lye mixture.
The alkali lye desulfurizer of 12. 1 kinds of liquefied petroleum gas (LPG), comprise alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), liquefied petroleum gas (LPG) intake pipeline (41) is connected with alkali lye desulfurization unit (301), alkali lye desulfurization unit (301) is connected with alkali liquid regeneration unit (302) through alkali lye intake pipeline (42), alkali liquid regeneration unit (302) returns alkali lye desulfurization unit through alkali lye return line (43), it is characterized in that, alkali lye return line (43) between alkali lye desulfurization unit (301) and alkali liquid regeneration unit (302) is provided with reductor intake pipeline (45), the intake pipeline (48) of alkali lye intake pipeline (46) or reductor and alkali lye mixture, liquefied petroleum gas (LPG) after alkali lye desulfurization is discharged through its export pipeline (44) and is collected product.
The alkali lye desulfurizer of 13. 1 kinds of liquefied petroleum gas (LPG), comprise alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), it is characterized in that, alkali lye return line (43) between described alkali lye desulfurization unit (301) and alkali liquid regeneration unit (302) is provided with alkali lye deacidification unit (303), described alkali lye deacidification unit (303) is provided with the intake pipeline (48) of reductor intake pipeline (45) or reductor and alkali lye mixture or reductor stationary installation (a) is set in alkali lye deacidification unit (303) inside.
The alkali lye desulfurizer of 14. 1 kinds of liquefied petroleum gas (LPG), comprise alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), liquefied petroleum gas (LPG) intake pipeline (41) is connected with alkali lye desulfurization unit (301), alkali lye desulfurization unit (301) is connected with alkali liquid regeneration unit (302) through alkali lye intake pipeline (42), alkali liquid regeneration unit (302) returns alkali lye desulfurization unit through alkali lye return line (43), it is characterized in that, alkali lye return line (43) between described alkali lye desulfurization unit (301) and alkali liquid regeneration unit (302) is provided with alkali lye deacidification unit (303), described alkali lye deacidification unit (303) arranges reductor intake pipeline (45), the intake pipeline (48) of alkali lye intake pipeline (46) or reductor and alkali lye mixture, or reductor stationary installation (a) is set in alkali lye deacidification unit (303) inside, liquefied petroleum gas (LPG) after alkali lye desulfurization is discharged through its export pipeline (44) and is collected product.
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