CN104371781A - Desulfurization method and device of liquefied petroleum gas - Google Patents
Desulfurization method and device of liquefied petroleum gas Download PDFInfo
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- CN104371781A CN104371781A CN201310353733.9A CN201310353733A CN104371781A CN 104371781 A CN104371781 A CN 104371781A CN 201310353733 A CN201310353733 A CN 201310353733A CN 104371781 A CN104371781 A CN 104371781A
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Abstract
The invention provides a desulfurization method and device of liquefied petroleum gas, the desulfurization method is as follows: contacting the liquefied petroleum gas with alcohol amine water solution with oxidizing substances removed, contacting the liquefied petroleum gas with lye with oxidizing substances removed, and collecting the liquefied petroleum gas product. The desulfurization method and device can avoid or reduce the generation of disulfides and polysulfides, and significantly improves the desulfurization efficiency of the desulfurization process, and after desulfurization, the content of the disulfides and polysulfides in the liquefied petroleum gas can be dramatically reduced.
Description
Technical field
The present invention relates to sulfur method and the device 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 petroleum gas (LPG), mercaptan in liquefied petroleum gas (LPG) 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 sulfur method and device of liquefied petroleum gas (LPG).
Sulfur method of the present invention comprises: after liquefied petroleum gas (LPG) contacts with the aqueous alkanolamine removing oxidizing substance, contacts with the alkali lye removing oxidizing substance, collects liquefied petroleum gas product.
The structure of described hydramine is: R
1r
2n-R
3, R
1, R
2, R
3hydrogen, C
1-C
4the alkyl of alkyl or hydroxyl, wherein at least one group is the alkyl containing a hydroxyl, and hydroxyl and atom N non-conterminous, Monoethanolamine MEA BASF (MEA), diethanolamine (DEA), diisopropanolamine (DIPA) (DIPA), N methyldiethanol amine (MDEA), N can be selected, one or more in N-diethylethanolamine (DEEA), N-ethyldiethanolamine (EDEA), monoisopropanolamine (MIPA) and tri-isopropanolamine (TIDP), one or more in preferred Monoethanolamine MEA BASF, diethanolamine, diisopropanolamine (DIPA) and N methyldiethanol amine.
Described hydramine accounts for 10 ~ 70% of aqueous alkanolamine total mass, and preferably 15 ~ 50%, most preferably 20 ~ 40%.
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 aqueous alkanolamine or alkali lye, gas phase oxygen and/or the oxide compound that generates in continuous hydramine desulfurization, alkali lye sulfur removal technology.In the desulfurization of continuous print hydramine, in alkali lye sulfur removal technology, due to aqueous alkanolamine, alkali lye constantly can contact extraneous oxygen, regenerate at hydramine, oxygen meeting and aqueous alkanolamine in alkali liquid regeneration process, alkali lye and the hydrocarbons carried secretly thereof, sulfide reaction generates peroxy acid, sulfurous acid, the oxide compounds such as-sulfinic acid, and these contain dissolved oxygen, the aqueous alkanolamine of gas phase oxygen and oxide compound, after alkali lye contacts with liquefied petroleum gas (LPG), can be the disulphide being difficult to remove by the mercaptan oxidation in liquefied petroleum gas (LPG), polysulfide also resides in liquefied petroleum gas (LPG), therefore only aqueous alkanolamine is removed, dissolved oxygen in alkali lye, gas phase oxygen and oxide compound, the desulfuration efficiency of sulfur removal technology could be improved, thoroughly remove the sulfide in liquefied petroleum gas (LPG).
The method contacting with reductor or mix can be adopted to remove oxidizing substance in aqueous alkanolamine and alkali lye respectively.Described reductor is the reducing substances that can not react with oxidizing substance generation redox reaction and with described aqueous alkanolamine or alkali lye.
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 aqueous alkanolamine and alkali lye, solid-state reductor and/or be insoluble to the solid-state reductor of aqueous alkanolamine and alkali lye.Aqueous alkanolamine or alkali lye can be adopted to remove oxidizing substance wherein with the method that the liquid state that can be dissolved in wherein and/or solid-state reductor mix mutually, and the method that aqueous alkanolamine or 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 aqueous alkanolamine and 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 aqueous alkanolamine or alkali lye.
The preferred add-on of described reductor is 0.1 ~ 200mg/kg of aqueous alkanolamine or alkali lye, most preferably 1 ~ 80mg/kg.
The content of described oxidizing substance in aqueous alkanolamine or alkali lye is generally more than 10mg/L; Remove after described oxidizing substance through the inventive method, in aqueous alkanolamine or 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.
Described aqueous alkanolamine, alkali lye contact with reductor or mix and preferably carries out in deacidification unit, the temperature of described deacidification unit preferably 10 ~ 80 DEG C, most preferably 30 ~ 60 DEG C.Described deacidification unit can be deoxidation tower or deoxidation still.
Liquefied petroleum gas (LPG) contacts with the aqueous alkanolamine removing oxidizing substance and hydramine desulphurization reaction occurs, and its preferred processing condition are as follows:
The volume ratio of described aqueous alkanolamine and liquefied petroleum gas (LPG) is 1:1 ~ 1:100, preferred 1:1 ~ 1:50; Contact Temperature is 10 ~ 80 DEG C, preferably 20 ~ 60 DEG C, most preferably 30 ~ 50 DEG C.
Described hydramine desulphurization reaction preferably carries out in the reactor.When hydramine 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.
Described aqueous alkanolamine can be reused after regeneration, and the object of regeneration removes hydrogen sulfide contact with liquefied petroleum gas (LPG) in aqueous alkanolamine afterwards, can remove hydrogen sulfide by ordinary methods such as heating.The preferred 105-130 DEG C of temperature of heating, the preferred 0.05-0.215MPa of pressure.
The liquefied petroleum gas (LPG) completing hydramine desulphurization reaction contacts with the alkali lye removing oxidizing substance and alkali lye desulphurization reaction occurs, and its processing condition 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.
The Contact Temperature of described alkali lye and liquefied petroleum gas (LPG) preferably 10 ~ 80 DEG C, most preferably 30 ~ 60 DEG C.
Described alkali lye desulphurization reaction preferably carries out at reactor.When alkali lye desulphurization reaction carries out in the reactor, volume space velocity preferably 0.1 ~ 20h 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 settlement separate sulfide and alkali lye that generate in oxidizing reaction, thus obtains the alkali lye without sulphur, makes alkali liquid regeneration.
The large gas of concentration of oxygen gas and/or hydrocarbon ils can also be added in above-mentioned aqueous alkanolamine or alkali lye, the oxidizing substance in above-mentioned aqueous alkanolamine or alkali lye can be removed so better.The gas preferred nitrogen that described concentration of oxygen gas is large and/or rare gas element, such as, in nitrogen, helium and argon gas one or more.Without the liquid hydrocarbon of sulphur under the preferred normal temperature and pressure of the hydrocarbon ils that described concentration of oxygen gas is large, such as, in gasoline, kerosene, diesel oil, hexane and heptane one or more, preferred sulphur content is at the liquid hydrocarbon of below 10ppm.Be separated gas phase and/or oil phase after above-mentioned gas and/or hydrocarbon ils mix with above-mentioned aqueous alkanolamine or alkali lye, remaining aqueous alkanolamine or alkali lye can enter desulfurization operations unit.Preferred 1:5 ~ the 5:1 of volume ratio of the add-on of described gas and aqueous alkanolamine or alkali lye, the preferred 1:1 ~ 1:50 of volume ratio of the add-on of hydrocarbon ils and aqueous alkanolamine or alkali lye.
The invention provides a kind of desulfurizer of liquefied petroleum gas (LPG), comprise hydramine desulfurization unit (101), alkali lye desulfurization unit 301, alkali liquid regeneration unit 302, it is characterized in that, in described hydramine desulfurization unit (101), be provided with the intake pipeline 28 of reductor intake pipeline 25 or reductor and aqueous alkanolamine mixture, the alkali lye return line 43 between described alkali lye desulfurization unit 301 and alkali liquid regeneration unit 302 be provided with the intake pipeline 48 of reductor intake pipeline 45 or reductor and alkali lye mixture.Described reductor preferably can be dissolved in the liquid deoxidizer of aqueous alkanolamine or alkali lye and/or solid-state reductor.
Desulfurizer schematic diagram of the present invention can see Fig. 1,2.
As Fig. 1, shown in 2, liquefied petroleum gas (LPG) intake pipeline 21 is connected with hydramine desulfurization unit 101, hydramine desulfurization unit 101 is connected with hydramine regeneration unit 102 through hydramine intake pipeline 22, hydramine regeneration unit 102 returns hydramine desulfurization unit through hydramine return line 23, hydramine intake pipeline 22 between hydramine desulfurization unit 101 and hydramine regeneration unit 102 or hydramine return line 23 are provided with reductor intake pipeline 25, the intake pipeline 28 of hydramine intake pipeline 26 or reductor and aqueous alkanolamine mixture, liquefied petroleum gas (LPG) after hydramine desulfurization enters alkali lye sulfur removal technology through liquefied petroleum gas (LPG) export pipeline 24 and 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 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 preferred desulfurizer of the present invention comprises hydramine desulfurization unit 101, hydramine regeneration unit 102, alkali lye desulfurization unit 301, alkali liquid regeneration unit 302, it is characterized in that, hydramine deacidification unit 103 is connected with between described hydramine desulfurization unit 101 and hydramine regeneration unit 102, described hydramine deacidification unit 103 is provided with reductor intake pipeline 25, or the intake pipeline 28 of reductor and aqueous alkanolamine mixture, or reductor stationary installation a is set in hydramine deacidification unit 103 inside, or reductor intake pipeline 25 is provided with in hydramine deacidification unit 103, hydrocarbon ils intake pipeline 27 or be provided with the shared intake pipeline 28 of reductor and hydrocarbon ils, 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 be 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, or in alkali lye deacidification unit 303, being provided with shared intake pipeline 48 or reductor intake pipeline 45, the hydrocarbon ils intake pipeline 47 of reductor and hydrocarbon ils.
The preferred reductor fixed bed of described reductor stationary installation a, preferably places the solid-state reductor being insoluble to aqueous alkanolamine or alkali lye, such as reducing metal and/or reductibility resin in described reductor stationary installation a.
When being provided with hydrocarbon ils intake pipeline in hydramine deacidification unit 103, the output terminal of described hydramine deacidification unit 103 preferably connects the separating unit 104 of hydramine and hydrocarbon ils.
When being provided with hydrocarbon ils intake pipeline in alkali lye deacidification unit 303, the output terminal of described alkali lye deacidification unit 303 preferably connects the separating unit 304 of alkali lye and hydrocarbon ils.
The preferred desulfurizer schematic diagram of the present invention can see Fig. 3,4.
As Fig. 3, shown in 4, liquefied petroleum gas (LPG) intake pipeline 21 is connected with hydramine desulfurization unit 101, hydramine desulfurization unit 101 is connected with hydramine regeneration unit 102 through hydramine intake pipeline 22, hydramine regeneration unit 102 returns hydramine desulfurization unit through hydramine return line 23, hydramine intake pipeline 22 between described hydramine desulfurization unit 101 and hydramine regeneration unit 102 or hydramine return line 23 are connected with hydramine deacidification unit 103, described hydramine deacidification unit 103 arranges reductor intake pipeline 25, the intake pipeline 28 of hydramine intake pipeline 26 or reductor and aqueous alkanolamine mixture, or reductor stationary installation a is set in hydramine deacidification unit 103 inside, hydrocarbon ils intake pipeline can also be provided with in described hydramine deacidification unit 103, the output terminal of hydramine deacidification unit 103 preferably connects the separating unit 104 of hydramine and hydrocarbon ils, liquefied petroleum gas (LPG) after hydramine desulfurization enters alkali lye sulfur removal technology through liquefied petroleum gas (LPG) export pipeline 24 and 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, also hydrocarbon ils intake pipeline can be set in alkali lye deacidification unit 303, the output terminal of described alkali lye deacidification unit 303 preferably connects the separating unit 304 of alkali lye and hydrocarbon ils, 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 lower to sulfur method of the present invention and device, and significantly improve the desulfuration efficiency of sulfur removal technology, after desulfurization, in liquefied petroleum gas (LPG), the content of disulphide, polysulfide 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.
Catalytic liquefied petroleum gas, takes from the stable liquid liquefied oil gas of the MIP technique of China Petrochemical Corp. subordinate refinery;
Coking liquefied petroleum gas (LPG), takes from the stable liquid liquefied oil gas of the delay coking process of China Petrochemical Corp. subordinate refinery;
Taihu Lake, Changzhou Nat Starch Chem Invest, hydramine sweetening agent SSH-3, main component is N methyldiethanol amine (MDEA).
The hydramine composite desulfurizing agent of Jiangsu innovation Chemical Co., Ltd., main component is N methyldiethanol amine.
Sulphur content before desulfurization, after desulfurization in liquefied petroleum gas (LPG) adopts SH/T0222 method to measure, and sulfur speciation distribution adopts GC-SCD method to measure.
Embodiment 1
Below in conjunction with Fig. 1, sulfur method of the present invention and device are described.
Catalytic liquefied petroleum gas to be desulfurization is the stable liquid liquefied oil gas taking from China Petrochemical Corp. subordinate refinery MIP technique.
The hydramine sweetening agent SSH-3 of Taihu Lake, Changzhou Chemical Co., Ltd. and distilled water are hybridly prepared into the aqueous alkanolamine that content is 30%, in aqueous alkanolamine, also add the DMKO solution that concentration is 50%, the add-on of solution is the 10mg/kg of aqueous alkanolamine.
The mixture of aqueous alkanolamine and DMKO solution enters hydramine desulfurization unit 101 through intake pipeline 28 and carries out desulfurization test with catalytic liquefied petroleum gas, the processing condition adopted are: counter current contact, Contact Temperature is 40 DEG C, the volume ratio of aqueous alkanolamine and liquefied petroleum gas (LPG) is 1:2.5, and during the liquid of catalytic liquefied petroleum gas, volume space velocity is 10h
-1.
Enter alkali lye desulfurization unit 301 through liquefied petroleum gas (LPG) export pipeline 24 after catalytic liquefied petroleum gas completes hydramine desulfurization and carry out alkali lye sulfur removal technology, described alkali lye desulfurization unit 301 is with churned mechanically reactor, the alkali lye used to be the sodium hydrate content taking from Sinopec refinery be 15% regeneration alkali lye, wherein the content of sulfonated phthalocyanine cobalt is 100mg/kg, the reductor employing concentration used is the DMKO solution of 50%, alkali lye, reductor injects alkali lye desulfurization unit 301 through the intake pipeline 48 of reductor and alkali lye mixture, contact with catalytic liquefied petroleum gas and carry out alkali lye desulfurization test, the processing condition adopted are: alkali lye, reductor and catalytic liquefied petroleum gas mechanical stirring in reactor mixes and contacts, 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.Finally discharge through export pipeline 44 through the liquefied petroleum gas product of alkali lye desulfurization, collect product.
Comparative example 1
Desulfurization test, with embodiment 1, does not just remove the process of oxidizing substance to aqueous alkanolamine, but directly uses aqueous alkanolamine to carry out desulfurization test to catalytic liquefied petroleum gas.
Comparative example 2
Desulfurization test, with embodiment 1, does not just remove the process of oxidizing substance to alkali lye, but directly uses alkali lye to carry out desulfurization test to catalytic liquefied petroleum gas.
Catalytic liquefied petroleum gas used and after embodiment 1, comparative example 1,2 desulfurization process the composition of liquefied petroleum gas (LPG) medium sulphide content in table 1.
Table 1
Embodiment 2
Below in conjunction with Fig. 3, sulfur method of the present invention and device are described.
Coking liquefied petroleum gas (LPG) to be desulfurization takes from the stable liquid liquefied oil gas of the delay coking process of China Petrochemical Corp. subordinate refinery.
The hydramine composite desulfurizing agent (main component is N methyldiethanol amine) Jiangsu being innovated Chemical Co., Ltd. is hybridly prepared into distilled water the aqueous alkanolamine that content is 28%.
Reductor fixed bed a is set in hydramine deacidification unit 103, loads Resorcinol resinoid in described reductor fixed bed a, make above-mentioned aqueous alkanolamine by hydramine deacidification unit 103, be less than 0.1mg/L by the content of oxidizing substance in rear aqueous alkanolamine.
Remove the aqueous alkanolamine after oxidizing substance and carry out desulfurization test from entering hydramine desulfurization unit 101 after hydramine deacidification unit 103 exports with coking liquefied petroleum gas (LPG), the processing condition adopted are: aqueous alkanolamine and liquefied petroleum gas (LPG) are in hydramine desulfurization unit counter current contact, Contact Temperature is 40 DEG C, the volume ratio of aqueous alkanolamine and liquefied petroleum gas (LPG) is 1:2.5, and during the liquid of coking liquefied petroleum gas (LPG), volume space velocity is 8h
-1.
Enter alkali lye desulfurization unit 301 through liquefied petroleum gas (LPG) export pipeline 24 after coking liquefied petroleum gas (LPG) completes hydramine desulfurization and carry out alkali lye sulfur removal technology, described alkali lye desulfurization unit 301 is packing tower, the alkali lye used to be the sodium hydrate content taking from Sinopec refinery be 15% regeneration alkali lye, wherein the content of sulfonated phthalocyanine cobalt is 100mg/kg, and the reductor used adopts concentration to be the hydrazine hydrate solution of 45%.Alkali lye injects alkali lye deacidification unit 303 through alkali lye intake pipeline 46, reductor through reductor intake pipeline 45, alkali lye desulfurization unit 301 is injected after mixing, contact with coking liquefied petroleum gas (LPG) and carry out alkali lye desulfurization test, the processing condition adopted are: alkali lye, reductor and coking liquefied petroleum gas (LPG) are in packing tower counter current contact, Contact Temperature is 42 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, and during the liquid of coking liquefied petroleum gas (LPG), volume space velocity is 10h
-1.Finally discharge through export pipeline 44 through the liquefied petroleum gas product of alkali lye desulfurization, collect product.
Comparative example 3
Desulfurization test, with embodiment 2, does not just remove the process of oxidizing substance to aqueous alkanolamine, but directly uses aqueous alkanolamine to carry out desulfurization test to coking liquefied petroleum gas (LPG).
Comparative example 4
Desulfurization test, with embodiment 2, does not just remove the process of oxidizing substance to alkali lye, but directly uses alkali lye to carry out desulfurization test to coking liquefied petroleum gas (LPG).
Coking liquefied petroleum gas (LPG) used and after embodiment 2, comparative example 3,4 desulfurization process the composition of liquefied petroleum gas (LPG) medium sulphide content in table 2.
Table 2
Claims (19)
1. a sulfur method for liquefied petroleum gas (LPG), comprising: after liquefied petroleum gas (LPG) contacts with the aqueous alkanolamine removing oxidizing substance, contacts with the alkali lye removing oxidizing substance, collects liquefied petroleum gas product.
2. in accordance with the method for claim 1, it is characterized in that, adopt the method contacting with reductor or mix to remove oxidizing substance in aqueous alkanolamine and alkali lye respectively.
3. in accordance with the method for claim 2, it is characterized in that, described reductor is the reducing substances that can not react with oxidizing substance generation redox reaction and with described aqueous alkanolamine or alkali lye, and described reductor is one or more in gaseous state reductor, liquid deoxidizer and solid-state reductor.
4. in accordance with the method for claim 3, it is characterized in that, described gaseous state reductor is H
2, CO, one or more in hydrazine.
5. in accordance with the method for claim 3, 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.
6. in accordance with the method for claim 3, 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.
7. in accordance with the method for claim 5, it is characterized in that, described reductibility resin be selected from hydroquinone type, sulfydryl class, pyridines and ferrocene resinoid one or more.
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. according to the method one of claim 2-8 Suo Shu, it is characterized in that, the add-on of described reductor is 0.1 ~ 200mg/kg of aqueous alkanolamine or alkali lye.
10. in accordance with the method for claim 9, it is characterized in that, it is as follows that liquefied petroleum gas (LPG) and the aqueous alkanolamine removing oxidizing substance contact the processing condition that desulphurization reaction occurs: the volume ratio of described aqueous alkanolamine and liquefied petroleum gas (LPG) is 1:1 ~ 1:100, and Contact Temperature is 10 ~ 80 DEG C.
11. according to method described in claim 10, reuses after it is characterized in that the regeneration of described aqueous alkanolamine.
12. in accordance with the method for claim 9, it is characterized in that, after liquefied petroleum gas (LPG) contacts with the aqueous alkanolamine removing oxidizing substance, to contact the processing condition that desulphurization reaction occurs as follows with the alkali lye removing oxidizing substance: 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.
13. in accordance with the method for claim 12, it is characterized in that, reuses after described alkali liquid regeneration.
14., according to the method one of claim 1-8 Suo Shu, is characterized in that, add the large gas of concentration of oxygen gas and/or hydrocarbon ils in described aqueous alkanolamine or alkali lye.
The desulfurizer of 15. 1 kinds of liquefied petroleum gas (LPG), comprise hydramine desulfurization unit (101), alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), it is characterized in that, in described hydramine desulfurization unit (101), be provided with the intake pipeline (28) of reductor intake pipeline (25) or reductor and aqueous alkanolamine mixture, the alkali lye return line (43) between described alkali lye desulfurization unit (301) and alkali liquid regeneration unit (302) be provided with the intake pipeline (48) of reductor intake pipeline (45) or reductor and alkali lye mixture.
The desulfurizer of 16. 1 kinds of liquefied petroleum gas (LPG), comprise hydramine desulfurization unit (101), alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), liquefied petroleum gas (LPG) intake pipeline (21) is connected with hydramine desulfurization unit (101), hydramine desulfurization unit (101) is connected with hydramine regeneration unit (102) through hydramine intake pipeline (22), hydramine regeneration unit (102) returns hydramine desulfurization unit through hydramine return line (23), it is characterized in that, hydramine intake pipeline (22) between hydramine desulfurization unit (101) and hydramine regeneration unit (102) or hydramine return line (23) are provided with reductor intake pipeline (25), the intake pipeline (28) of hydramine intake pipeline (26) or reductor and aqueous alkanolamine mixture, liquefied petroleum gas (LPG) after hydramine desulfurization enters alkali lye sulfur removal technology through liquefied petroleum gas (LPG) export pipeline (24) and 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 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 desulfurizer of 17. 1 kinds of liquefied petroleum gas (LPG), comprise hydramine desulfurization unit (101), hydramine regeneration unit (102), alkali lye desulfurization unit (301), alkali liquid regeneration unit (302), it is characterized in that, hydramine deacidification unit (103) is connected with between described hydramine desulfurization unit (101) and hydramine regeneration unit (102), described hydramine deacidification unit (103) is provided with reductor intake pipeline (25), or the intake pipeline of reductor and aqueous alkanolamine mixture (28), or reductor stationary installation (a) is set in hydramine deacidification unit (103) inside, or reductor intake pipeline (25) is provided with in hydramine deacidification unit (103), hydrocarbon ils intake pipeline (27) or be provided with the shared intake pipeline (28) of reductor and hydrocarbon ils, 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) be 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, or in alkali lye deacidification unit (303), being provided with shared intake pipeline (48) or reductor intake pipeline (45), the hydrocarbon ils intake pipeline (47) of reductor and hydrocarbon ils.
18., according to device according to claim 17, is characterized in that, when being provided with hydrocarbon ils intake pipeline in hydramine deacidification unit (103), the output terminal of described hydramine deacidification unit (103) connects the separating unit (104) of hydramine and hydrocarbon ils.
19., according to device according to claim 17, is characterized in that, when being provided with hydrocarbon ils intake pipeline in alkali lye deacidification unit (303), the output terminal of described alkali lye deacidification unit (303) connects the separating unit (304) of alkali lye and hydrocarbon ils.
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| CN110628476A (en) * | 2018-06-21 | 2019-12-31 | 中国石油化工股份有限公司 | Pretreatment method and purifying agent for refinery rich gas and desulfurization method for dry gas and/or liquefied gas |
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