CN101993750B - Method for refining liquefied petroleum gas - Google Patents

Method for refining liquefied petroleum gas Download PDF

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CN101993750B
CN101993750B CN 201010562891 CN201010562891A CN101993750B CN 101993750 B CN101993750 B CN 101993750B CN 201010562891 CN201010562891 CN 201010562891 CN 201010562891 A CN201010562891 A CN 201010562891A CN 101993750 B CN101993750 B CN 101993750B
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China
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liquefied petroleum
petroleum gas
mercaptan
lpg
removal agent
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CN 201010562891
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Chinese (zh)
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CN101993750A (en
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柯明
蒋庆哲
宋昭峥
王雨
史丽娟
张振全
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中国石油大学(北京)
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Abstract

The invention discloses a method for refining liquefied petroleum gas, which is characterized by comprising the following steps of: mixing a liquefied petroleum gas raw material to be refined and alkylol amine liquid together; entering a carbonyl sulfide hydrolysis reactor and removing carbonyl sulfide and hydrothion out of the liquefied petroleum gas under the joint action of a carbonyl sulfide hydrolysis catalyst and the alkylol amine liquid; introducing the liquefied petroleum gas without carbonyl sulfide and hydrothion into an extraction tower to contact a mercaptan removing agent water solution for removing mercaptan out of the liquefied petroleum gas; separating the liquefied petroleum gas from the mercaptan removing agent water solution, and washing with water and then recycling; stripping the mercaptan removing agent water solution with the mercaptan absorbed from the liquefied petroleum gas in a stripping tower for removing the mercaptan to realize regeneration and recycling.The method remarkably lightens the environmental protection stress of refineries without using a sodium hydroxide solution and discharging slag and achieves the advantage of simple operation process;in addition, the used mercaptan removing agent is stripped for being regenerated without using an oxidant, and the total sulphur content of the liquefied petroleum gas can be reduced to below 5 microgram.gram-1.

Description

A kind of process for purification of liquefied petroleum gas (LPG)
Technical field
The invention belongs to petrochemical industry, particularly liquefied petroleum gas (LPG) removes the process for purification of hydrogen sulfide, carbonylsulfide, mercaptan sulfides.
Background technology
Along with the increase of import high-sulfur crude oil amount of finish and the increase of residual oil oil refining ratio, total sulfur content also increases in the liquefied petroleum gas (LPG) (LPG) that devices such as refinery catalytic cracking are produced.Usually contain H in the liquefied petroleum gas (LPG) 2S, COS, CS 2, poisonous and harmful element, particularly H wherein such as mercaptan, thioether and disulphide 2S, COS and mercaptan endanger greatlyyer, as not removing, can cause great pollution to environment, also can produce greatly influence to the following process process.
Current liquefied gas process for refining mainly is: the liquefied gas that comes out from refinery's device, at first enter hydramine and wash tower, remove a large amount of hydrogen sulfide with reproducible alkanolamine solution, then through the liquid base caustic prescrub, remove residual a small amount of hydrogen sulfide, enter extraction tower at last, with agent alkali lye extracting mercaptan, obtain the neutral solution gasification after the washing, the alkali liquor oxidized regeneration of agent.The shortcoming of this technology is: whole technology is used caustic liquid alkali in a large number, and alkali lye is changed frequent, causes waste lye to discharge to environmental protection and brings very big pressure, and spent lye treatment has also increased the production cost of refinery; The desulfuration of liquefied gas degree of depth is not high, does not consider removing of one of principal pollutant COS; Disulphide in the oxidation regeneration agent alkali is difficult to tell, and the total sulfur content in the liquefied petroleum gas (LPG) is exceeded standard.
Chinese patent CN200910250279, a kind of doctor process of liquid hydrocarbon, be to adopt liquid-liquor alkali extraction process to carry out mercaptan removal liquid hydrocarbon, agent alkali refers to by liquid caustic soda or the alkali lye that added function intensified auxiliary agent as extractant, and function intensified auxiliary agent is selected from the organic compound that has hydroxyl, ketone group or carboxyl and in the quaternary ammonium material one or more.
CN200510132103, a kind of method of liquefied gas refining desulfurization, it is characterized in that: liquefied gas enters the further air sweetening of air sweetening tower again with after catalyzer-alkali lye and the air mixed after the pre-desulfurization, and liquefied gas enters separating tank and separates the smart filter of laggard sand tower then.
CN200510126054, catalyst for mercaptol oxidization, its preparation and application, this invention provides a kind of method of mercaptan oxidation, is in the presence of oxygen and basic solution medium, and hydrocarbon stream is contacted with the mercaptan catalyzer of this invention.
CN200510072353, a kind of method of refining catalytic liquefied petroleum gas is characterized in that: step 1. in the active ingredient of used hydrolytic catalyst of carbonyl sulfur be sodium hydroxide or potassium hydroxide, or sodium hydroxide and potassium hydroxide, its carrier is γ-Al 2O 3
CN200480010360, WO2004091754, US2006188424, a kind of from comprising H 2Remove H in the air-flow of S and mercaptan compound 2The method of S and mercaptan, this method makes air-flow at H 2S-removes and contacts with the first aqueous base washings in the section and remove H from air-flow 2S makes poor H 2The air-flow of S contacts with the second aqueous base washings at mercaptan-remove in the section.
CN02156879, adopt solid alkali and agent-alkali to the combined method of liquefied petroleum gas (LPG) and lighter hydrocarbons deep desulfuration, be in the sulfur removal technology of liquefied petroleum gas (LPG) and lighter hydrocarbons, the method for solid alkali desulfurization and agent-alkali desulfurization to be combined, it is characterized in that it being that pending raw material is carried out desulfurization, mercaptan removal by liquid base cleaning of evaporator or solid soda-wash tower, the reverse extraction tower of liquid-liquid or liquid-liquid static mixer successively.
JP2005239943, except the method and apparatus of mercaptan, feature is with alkaline solution refined solution liquefied oil gas LPG in purification tower.
US6485697, this removes the method for sulfocompound and carbonic acid gas from gaseous mixture, and this method is used alkali lye mixture continuous adsorption technology, removes H from sour gas 2S.
US5104630 removes the technology of carbonylsulfide from the hydrocarbon incoming flow, in this technology, cos conversion becomes carbonic acid gas and hydrogen sulfide to carry out in the presence of alkaline aqueous solution.
US4880606, for the method and apparatus of sulfur-bearing or hydrogen sulfide desulfurization, preferred washings is to use the alkali lye of 1,4-naphthoquinones-2-sodium sulfonate catalyzer.
US4104155, feature is to use the alkali lye extracting mercaptan behind the stripping.
More than these patents all do not solve the waste lye problem of environment pollution caused.
Summary of the invention
The process for purification that the purpose of this invention is to provide a kind of liquefied petroleum gas (LPG) is to remove the impurity such as carbonylsulfide, hydrogen sulfide and mercaptan in the liquefied petroleum gas (LPG).
The process for purification of a kind of liquefied petroleum gas (LPG) of the present invention is characterized in that comprising the steps:
(a) raw liquefied petroleum gas to be made with extra care is mixed with hydramine liquid, enters cos hydrolysis reactor, under the acting in conjunction of hydrolytic catalyst of carbonyl sulfur and hydramine liquid, the carbonylsulfide in the liquefied petroleum gas (LPG) and hydrogen sulfide is removed;
(b) liquefied petroleum gas (LPG) that removes behind carbonylsulfide and the hydrogen sulfide enters extraction tower, contacts with the mercaptan removal agent aqueous solution, removes the mercaptan in the liquefied petroleum gas (LPG);
(c) liquefied petroleum gas (LPG) is separated with the mercaptan removal agent aqueous solution, reclaims after washing;
(d) with b) mercaptan removal agent aqueous solution stripping in stripping tower in the absorption raw liquefied petroleum gas in the step behind the mercaptan, remove mercaptan regeneration, the mercaptan removal agent aqueous solution that removes after the mercaptan regeneration is recycled to b) extraction tower of step, recycle.
The invention is characterized in: the service temperature in the described carbonyl sulfide hydrolysis reaction is 20 ℃~50 ℃, and pressure is 0.8MPa~1.5MPa, and volume space velocity is 1h -1~10h -1
The invention is characterized in: described hydrolytic catalyst of carbonyl sulfur is by active ingredient Cs 2O, K 2O, Na 2O, SrO, BaO, CaO, MgO, ZnO, Fe 2O 3, MoO 3, Re 2O 3, several catalyzer of forming on the carrier that load among the PbS, carrier is selected from γ-Al 2O 3Or γ-Al 2O 3+ TiO 2Complex carrier, the weight of described active ingredient is the 1wt%~40wt% of total catalyst weight.
The invention is characterized in: described hydramine liquid is the aqueous solution of hydramine, hydramine is selected from a kind of in Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine and the diisopropanolamine (DIPA) or their mixture, the concentration of hydramine liquid is 10wt%~50wt%, and the add-on of hydramine is the 0.5wt%~15wt% of raw material.
The invention is characterized in: the service temperature of the extraction tower that described liquefied petroleum gas (LPG) contacts with the mercaptan removal agent aqueous solution is 10 ℃~50 ℃, working pressure 0.8MPa~2.0MPa, and the mercaptan removal agent is 0.5~10: 1 with the ratio of liquefied petroleum gas (LPG).
The invention is characterized in: the described mercaptan removal agent aqueous solution contains two kinds of components, first component is selected from quaternary ammonium hydroxide with the mixture of one or more in the quaternary phosphonium hydroxide, second component is selected from one or more the mixture in Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine, diisopropanolamine (DIPA), quadrol, propylene diamine, butanediamine, N-N-formyl morpholine N-, N-Methyl pyrrolidone, methyl alcohol, ethanol and the ethylene glycol, in the mercaptan removal agent aqueous solution, first component concentrations is 0.1wt%~50wt%, and second concentration of component is 0.1wt%~98wt%.
The invention is characterized in: the operational condition of the steam stripping regeneration of the described mercaptan removal agent aqueous solution in stripping tower is: 80 ℃~130 ℃ of temperature, pressure 0.1MPa~0.6MPa.
Describe technical scheme of the present invention in detail below in conjunction with technical process.
In view of the refining alkali lye problem of environment pollution caused that occurs of liquefied petroleum gas (LPG), the inventor proposes: (1) combines hydrolysis and the hydramine depriving hydrogen sulphide of carbonylsulfide COS, can realize COS one one-step hydrolysis, takes off H simultaneously 2S replaces pre-alkali liquid washing; (2) remove mercaptan in the liquefied petroleum gas (LPG) with mercaptan removal agent extracting, liquefied petroleum gas (LPG) namely reaches the desulfurization requirement through washing, the mercaptan removal agent of being rich in mercaptan namely can be recycled by 80~130 ℃ of steam stripping regenerations in stripping tower, and the sulfur-bearing tail gas that stripping comes out is sent into hydrogenating desulfurization system or sulfur recovery system by press.Because the mercaptan removal agent can be recycled, can reduce the discharging of waste liquid more than 95%, mercaptan removal is effective, the total sulfur content that the solves liquefied petroleum gas (LPG) simultaneously problem that exceeds standard.
Process description is as follows.Liquefied petroleum gas (LPG) after process hydramine liquid is washed, the hydrogen sulfide of residual minim also, the carbonylsulfide in the liquefied gas and hydrogen sulfide are under the acting in conjunction of hydrolytic catalyst of carbonyl sulfur and poor mercaptan amine liquid, carbonylsulfide and hydrogen sulfide are removed, and its ultimate principle can be represented with following chemical equation:
* R and R ' organic group
Liquefied petroleum gas (LPG) after fixed bed takes off carbonylsulfide and hydrogen sulfide, with the mercaptan removal sweetening agent mercaptan in the liquefied gas is extracted, the mercaptan removal agent of being rich in mercaptan namely can be recycled by 80~130 ℃ of steam stripping regenerations, and the sulfur-bearing tail gas that stripping comes out is sent into hydrogenating desulfurization system or sulfur recovery system by compressor.Its ultimate principle can be represented with following chemical equation:
" be organic group, wherein R ' is quaternary ammonium cation for R, R ' and R
The hydrolytic catalyst of carbonyl sulfur that the present invention adopts is by active ingredient Cs 2O, K 2O, Na 2O, SrO, BaO, CaO, MgO, ZnO, Fe 2O 3, MoO 3, Re 2O 3, several catalyzer of forming on the carrier that load among the PbS, carrier is selected from γ-Al 2O 3Or γ-Al 2O 3+ TiO 2Complex carrier, the content of described active ingredient is the 1wt%~40wt% of total catalyst weight.The hydramine sweetening agent is selected from a kind of of Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine and diisopropanolamine (DIPA) or their several mixtures.The concentration of hydramine desulfurization agent aqueous solution is 10wt%~50wt%.Hydramine sweetening agent add-on is the 0.5wt%~15wt% of raw material.The temperature of reaction of cos hydrolysis reactor is 20 ℃~50 ℃, and working pressure 0.8MPa~1.5MPa, volume space velocity are 1h -1~10h -1
Mercaptan removal agent of the present invention is made up of two kinds of components: first component is selected from quaternary ammonium hydroxide with the mixture of one or more in the quaternary phosphonium hydroxide; Second component is selected from one or more the mixture in Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine, diisopropanolamine (DIPA), quadrol, propylene diamine, butanediamine, N-N-formyl morpholine N-, N-Methyl pyrrolidone, methyl alcohol, ethanol and the ethylene glycol.In the mercaptan removal agent aqueous solution, first concentration of component is 0.1wt%~50wt%, and the second class concentration of component is 0.1wt%~98wt%.The operational condition of extraction tower: temperature is 10 ℃~50 ℃, pressure 0.8MPa~2.0MPa, and the mercaptan removal agent is 0.5~10: 1 with the ratio of liquefied petroleum gas (LPG).The condition of mercaptan removal agent steam stripping regeneration is: 80 ℃~130 ℃ of temperature, pressure 0.1MPa~0.6MPa.
The first component quaternary ammonium hydroxide of mercaptan removal agent is with quaternary phosphonium hydroxide, it is characterized in that being selected from the quaternary ammonium hydroxide of following structure with one or more mixture in the quaternary phosphonium hydroxide:
(1) hydroxide N, N-dialkylimidazolium ammonium: Wherein R can be C 1~C 18Alkyl or (n is 1~6 integer).
(2) hydroxide N-alkyl pyridine ammonium: Wherein R can be C 1~C 18Alkyl or (n is 1~6 integer
(3) quaternary ammonium alkyl alkali:
With R wherein 1, R 2, R 3And R 4Be respectively C 1~C 18Alkyl or (n is 1~6 integer), they can be the same or different.
(4) Wan Ji quaternary phosphonium hydroxide:
With R wherein 1, R 2, R 3And R 4Be respectively C 1~C 18Alkyl or (n is 1~6 integer), they can be the same or different.
A kind of liquefied petroleum gas (LPG) process for purification of the present invention compared with prior art has the following advantages:
1, because sodium hydroxide solution is not used in the mercaptan removal agent, can be recycled simultaneously, no alkaline residue discharging significantly alleviates the pressure of refinery environmental protection;
2, technological operation is easy, is applicable to that the liquefied petroleum gas (LPG) of each device production of refinery is refining;
3, oxygenant is not used in not aerobicization regeneration of mercaptan removal agent, has eliminated potential safety hazard;
4, can produce the oil liquefied gas of non-corrosiveness super low sulfur, the liquefied petroleum gas (LPG) total sulfur content can be down to 5 μ gg-1 even lower.
Description of drawings
Fig. 1 is the process flow diagram of liquefied petroleum gas (LPG) process for purification of the present invention.
Wherein, 1-hydramine liquid is washed back liquefied petroleum gas (LPG), 2-poor mercaptan amine liquid, 3-poor mercaptan amine liquid pump, 4-static mixer A, 5-cos hydrolysis reactor, 6-hydramine liquid slurry tank, the rich mercaptan amine of 7-liquid, 8-extraction tower, 9-desulfurization agent aqueous solution slurry tank, 10-removes the sweetening agent stripping tower, the 11-waterline, 12-washes pump, 13-static mixer B, 14-water washing tank, 15-washes sewage, removes acidic water stripping device, the refining back of 16-liquefied petroleum gas (LPG), the rich sulphur mercaptan removal of the 17-agent aqueous solution, 18-heat exchanger, 19-stripping tower, the 20-water cooler, 21-return tank, 22-sulfur-bearing tail gas, the 23-reflux pump, the 24-reboiler, 25-steam, the poor sulphur mercaptan removal of the 26-agent aqueous solution, the water-soluble liquid pump of the poor sulphur mercaptan removal of 27-agent, 28-mercaptan removal agent aqueous solution water cooler, 29-surge tank, the poor mercaptan removal agent of 30-aqueous solution transfer pump.
Idiographic flow is as follows: the liquefied petroleum gas (LPG) after washing from hydramine (not washing) 1, mix the cos hydrolysis reactor 5 that enters together through static mixer 4 with the poor mercaptan amine liquid 2 that poor mercaptan amine liquid pump 3 is sent here.Prefabricated hydrolytic catalyst of carbonyl sulfur and the porcelain ball that is used for supporting hydrolyst are housed in this reactor, in reactor, under the acting in conjunction of hydrolytic catalyst of carbonyl sulfur and poor mercaptan amine liquid, the carbonylsulfide in the liquefied petroleum gas (LPG) and hydrogen sulfide are removed.Certainly compressed into into hydramine liquid slurry tank 6 by the liquefied petroleum gas (LPG) that cos hydrolysis reactor 5 is come out, the rich mercaptan amine liquid of deviating from 7 goes the regeneration of hydramine liquid, certainly compressed into into extraction tower 8 bottoms and reverse contact of being sent here by poor sulphur mercaptan removal agent aqueous solution transfer pump 30 of the poor sulphur mercaptan removal agent aqueous solution (temperature is lower than 40 ℃) by the liquefied petroleum gas (LPG) that hydramine liquid slurry tank 6 comes out, remove the mercaptan in the liquefied gas.Taken off the liquefied petroleum gas (LPG) of mercaptan from compressing into into mercaptan removal agent aqueous solution slurry tank 9, remove the mercaptan removal agent aqueous solution that carries, it merges through pipeline 10 and the rich sulphur mercaptan removal agent aqueous solution, the liquefied petroleum gas (LPG) of being come out by mercaptan removal agent aqueous solution slurry tank 9 enters water washing tank 14 from pressing the water of sending here with water Xian pump 12 to be mixed through static mixer 13, remove the mercaptan removal agent that liquefied petroleum gas (LPG) is carried through washing, the sour water 15 that water washing tank 14 is told removes acidic water stripping device, and the refining back liquefied petroleum gas (LPG) 16 that is gone out by water washing tank 14 is from extruding device.The rich sulphur mercaptan removal agent aqueous solution 17 carries out heat exchange through the poor sulphur mercaptan removal agent aqueous solution with heat and enters stripping tower 19 tops, the steam that is produced by reboiler 24 carries out stripping to the rich sulphur mercaptan removal agent aqueous solution, the stripping temperature is 80 ℃~130 ℃, pressure 0.1MPa~0.6MPa.The mercaptan mixed gas that contains that stripping comes out is come out by stripping tower 19 tops, enter return tank 21 through water cooler 20 coolings, send into hydrogenating desulfurization system or sulfur recovery system by the sulfur-bearing tail gas 22 that return tank 21 is told by compressor, return tank divides water outlet and mercaptan removal agent to return the stripping tower top by returning sulphur pump 23 as backflow.The poor sulphur mercaptan removal agent aqueous solution 26 behind the stripping, is cooled to send into surge tank 29 below 40 ℃ through heat exchanger 18 and 28 coolings of poor sulphur mercaptan removal agent aqueous solution water cooler by the water-soluble liquid pump 27 of poor sulphur mercaptan removal agent, namely finishes whole liquefied petroleum gas (LPG) treating process.
Embodiment
Embodiment 1
Raw material is for containing 12 μ gg-1 hydrogen sulfide sulphur, 15 μ gg-1 carbonylsulfide sulphur and 125 μ gg-1 mercaptan sulfurs, the liquefied petroleum gas (LPG) of thiomethyl alcohol sulphur 113 μ gg-1, sulfur alcohol sulphur 12 μ gg-1 wherein, treatment step comprises: (1) is sweetening agent with the Monoethanolamine MEA BASF of 15wt%, add-on is the 2wt% of liquefied petroleum gas (LPG) gross weight, the temperature of reaction of cos hydrolysis reactor is 30 ℃, pressure is 0.8MPa, and the volume space velocity by the hydrolytic catalyst of carbonyl sulfur bed is 6h -1, hydrolytic catalyst of carbonyl sulfur is MgO/ γ-Al 2O 3(2) when extraction desulfurization alcohol, used mercaptan removal agent is the aqueous solution that contains tetramethylammonium hydroxide 10wt% and Monoethanolamine MEA BASF 10wt%, the mercaptan removal agent is 6: 1 with the ratio of liquefied petroleum gas (LPG), temperature is 30 ℃, and pressure is 0.8MPa, and liquefied petroleum gas (LPG) is by after washing, hydrogen sulfide sulphur is 0 μ gg-1, carbonylsulfide sulphur 0.01 μ gg-1, mercaptan sulfur are 0 μ gg-1, and refining back liquefied petroleum gas (LPG) total sulfur content is 1.5 μ gg-1; (3) rich sulphur mercaptan removal agent aqueous solution steam stripping regeneration, the stripping tower operational condition: working pressure is 0.2MPa, column bottom temperature is 120 ℃, 100 ℃ of tower top temperatures.
Embodiment 2
Raw material is for containing 15 μ gg-1 hydrogen sulfide sulphur, 11 μ gg-1 carbonylsulfide sulphur and 218 μ gg-1 mercaptan sulfurs, the liquefied petroleum gas (LPG) of thiomethyl alcohol sulphur 199 μ gg-1, sulfur alcohol sulphur 19 μ gg-1 wherein, treatment step comprises: (1) is sweetening agent with the methyldiethanolamine of 25wt%, add-on is the 5wt% of liquefied petroleum gas (LPG) gross weight, the temperature of reaction of cos hydrolysis reactor is 40 ℃, pressure is 1.2MPa, and is logical
The volume space velocity of crossing the hydrolytic catalyst of carbonyl sulfur bed is 6h -1, hydrolytic catalyst of carbonyl sulfur is (MgO+CaO)/(γ-Al 2O 3+ TiO 2); (2) when extraction desulfurization alcohol, used mercaptan removal agent is the aqueous solution that contains hydroxide dimethyl ethyl ethylbenzene base ammonium 20wt% and Monoethanolamine MEA BASF 10wt%, the mercaptan removal agent is 5: 1 with the ratio of liquefied petroleum gas (LPG), temperature is 40 ℃, and pressure is 0.8MPa, and liquefied petroleum gas (LPG) is by after washing, hydrogen sulfide sulphur is 0 μ gg-1, carbonylsulfide sulphur 0 μ gg-1, mercaptan sulfur are 0 μ gg-1, and refining back liquefied petroleum gas (LPG) total sulfur content is 2.5 μ gg-1; (3) rich sulphur mercaptan removal agent aqueous solution steam stripping regeneration, the stripping tower operational condition: working pressure is 0.2MPa, column bottom temperature is 120 ℃, 100 ℃ of tower top temperatures.
Embodiment 3
Raw material is for containing 15 μ gg-1 hydrogen sulfide sulphur, 11 μ gg-1 carbonylsulfide sulphur and 218 μ gg-1 mercaptan sulfurs, the liquefied petroleum gas (LPG) of thiomethyl alcohol sulphur 199 μ gg-1, sulfur alcohol sulphur 19 μ gg-1 wherein, treatment step comprises: (1) is sweetening agent with the methyldiethanolamine of 25wt%, add-on is the 5wt% of liquefied petroleum gas (LPG) gross weight, the temperature of reaction of cos hydrolysis reactor is 40 ℃, pressure is 1.2MPa, and the volume space velocity by the hydrolytic catalyst of carbonyl sulfur bed is 6h -1, hydrolytic catalyst of carbonyl sulfur is MgO/ (γ-Al 2O 3+ TiO 2); (2) when extraction desulfurization alcohol, used mercaptan removal agent is the aqueous solution that contains hydroxide N-methyl-N-ethyl imidazol(e) ammonium 10wt% and diglycolamine 15wt%, the mercaptan removal agent is 5: 1 with the ratio of liquefied petroleum gas (LPG), temperature is 40 ℃, and pressure is 0.8MPa, and liquefied petroleum gas (LPG) is by after washing, hydrogen sulfide sulphur is 0 μ gg-1, carbonylsulfide sulphur 0 μ gg-1, mercaptan sulfur are 0 μ gg-1, and refining back liquefied petroleum gas (LPG) total sulfur content is 2.5 μ gg-1; (3) rich sulphur mercaptan removal agent aqueous solution steam stripping regeneration, the stripping tower operational condition: working pressure is 0.2MPa, column bottom temperature is 120 ℃, 100 ℃ of tower top temperatures.
Embodiment 4
Raw material is for containing 9 μ gg-1 hydrogen sulfide sulphur, 17 μ gg-1 carbonylsulfide sulphur and 367 μ gg-1 mercaptan sulfurs, the liquefied petroleum gas (LPG) of thiomethyl alcohol sulphur 329 μ gg-1, sulfur alcohol sulphur 38 μ gg-1 wherein, treatment step comprises: (1) is sweetening agent with the methyldiethanolamine of 25wt%, add-on is the 5wt% of liquefied petroleum gas (LPG) gross weight, the temperature of reaction of cos hydrolysis reactor is 20 ℃, pressure is 1.2MPa, and the volume space velocity by the hydrolytic catalyst of carbonyl sulfur bed is 6h -1, hydrolytic catalyst of carbonyl sulfur is MgO/ (γ-Al 2O 3+ TiO 2); (2) when extraction desulfurization alcohol, used mercaptan removal agent is the aqueous solution that contains hydroxide N-normal-butyl pyridine ammonium 18wt% and diglycolamine 15wt%, the mercaptan removal agent is 4: 1 with the ratio of liquefied petroleum gas (LPG), temperature is 20 ℃, and pressure is 0.8MPa, and liquefied petroleum gas (LPG) is by after washing, hydrogen sulfide sulphur is 0 μ gg-1, carbonylsulfide sulphur 0 μ gg-1, mercaptan sulfur are 1.2 μ gg-1, and refining back liquefied petroleum gas (LPG) total sulfur content is 3.8 μ gg-1; (3) rich sulphur mercaptan removal agent aqueous solution steam stripping regeneration, the stripping tower operational condition: working pressure is 0.32MPa, column bottom temperature is 120 ℃, 100 ℃ of tower top temperatures.
Embodiment 5
Raw material is for containing 9 μ gg-1 hydrogen sulfide sulphur, 17 μ gg-1 carbonylsulfide sulphur and 367 μ gg-1 mercaptan sulfurs, the liquefied petroleum gas (LPG) of thiomethyl alcohol sulphur 329 μ gg-1, sulfur alcohol sulphur 38 μ gg-1 wherein, treatment step comprises: (1) is sweetening agent with the methyldiethanolamine of 25wt%, add-on is the 5wt% of liquefied petroleum gas (LPG) gross weight, the temperature of reaction of cos hydrolysis reactor is 20 ℃, pressure is 1.2MPa, and the volume space velocity by the hydrolytic catalyst of carbonyl sulfur bed is 6h -1, hydrolytic catalyst of carbonyl sulfur is MgO/ (γ-Al 2O 3+ TiO 2); (2) when extraction desulfurization alcohol, used mercaptan removal agent is the aqueous solution that contains tetramethylphosphonihydroxide hydroxide Ji Phosphonium 20wt% and Monoethanolamine MEA BASF 15wt%, the mercaptan removal agent is 4: 1 with the ratio of liquefied petroleum gas (LPG), temperature is 20 ℃, and pressure is 0.8MPa, and liquefied petroleum gas (LPG) is by after washing, hydrogen sulfide sulphur is 0 μ gg-1, carbonylsulfide sulphur 0 μ gg-1, mercaptan sulfur are 1.5 μ gg-1, and refining back liquefied petroleum gas (LPG) total sulfur content is 4.1 μ gg-1; (3) rich sulphur mercaptan removal agent aqueous solution steam stripping regeneration, the stripping tower operational condition: working pressure is 0.2MPa, column bottom temperature is 120 ℃, 100 ℃ of tower top temperatures.

Claims (7)

1. the process for purification of a liquefied petroleum gas (LPG) is characterized in that comprising the steps:
(a) raw liquefied petroleum gas to be made with extra care is mixed with hydramine liquid, enters cos hydrolysis reactor, under the acting in conjunction of hydrolytic catalyst of carbonyl sulfur and hydramine liquid, the carbonylsulfide in the liquefied petroleum gas (LPG) and hydrogen sulfide is removed;
(b) liquefied petroleum gas (LPG) that removes behind carbonylsulfide and the hydrogen sulfide enters extraction tower, contacts with the mercaptan removal agent aqueous solution, removes the mercaptan in the liquefied petroleum gas (LPG);
(c) liquefied petroleum gas (LPG) is separated with the mercaptan removal agent aqueous solution, reclaims after washing;
(d) with b) mercaptan removal agent aqueous solution stripping in stripping tower in the absorption raw liquefied petroleum gas in the step behind the mercaptan, remove mercaptan regeneration, the mercaptan removal agent aqueous solution that removes after the mercaptan regeneration is recycled to b) extraction tower of step, recycle;
The described mercaptan removal agent aqueous solution contains two kinds of components, first component is selected from quaternary ammonium hydroxide with the mixture of one or more in the quaternary phosphonium hydroxide, and second component is selected from one or more the mixture in Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine, diisopropanolamine (DIPA), quadrol, propylene diamine, butanediamine, N-N-formyl morpholine N-, N-Methyl pyrrolidone, methyl alcohol and the ethanol;
The first component quaternary ammonium hydroxide of mercaptan removal agent is with quaternary phosphonium hydroxide, it is characterized in that being selected from the quaternary ammonium hydroxide of following structure with one or more mixture in the quaternary phosphonium hydroxide:
(1) hydroxide N, N-dialkylimidazolium ammonium: Wherein R is H (n is 1~6 integer);
(2) hydroxide N-alkyl pyridine ammonium: Wherein R is (n is 1~6 integer);
(3) quaternary ammonium alkyl alkali:
R wherein 1Be C 1~C 18Alkyl, R 2, R 3And R 4Be respectively (n is 1~6 integer), they can be the same or different;
(4) Wan Ji quaternary phosphonium hydroxide:
R wherein 1Be C 1~C 18Alkyl, R 2, R 3And R 4Be respectively (n is 1~6 integer), they can be the same or different.
2. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: the service temperature in the described cos hydrolysis reactor is 20 ℃~50 ℃, and pressure is 0.8MPa~1.5MPa, and volume space velocity is 1h -1~10h -1
3. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: described hydrolytic catalyst of carbonyl sulfur is by active ingredient SrO, BaO, CaO, MgO, ZnO, Fe 2O 3, MoO 3, several catalyzer of forming on the carrier that load among the PbS, carrier is selected from γ-Al 2O 3Or γ-Al 2O 3+ TiO 2Complex carrier, the weight of described active ingredient is the 1wt%~40wt% of total catalyst weight.
4. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: described hydramine liquid is the aqueous solution of hydramine, hydramine is selected from a kind of in Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, diglycolamine and the diisopropanolamine (DIPA) or their mixture, the concentration of hydramine liquid is 10wt%~50wt%, and the add-on of hydramine is the 0.5wt%~15wt% of raw material.
5. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: the service temperature of the extraction tower that described liquefied petroleum gas (LPG) contacts with the mercaptan removal agent aqueous solution is 10 ℃~50 ℃, pressure 0.8MPa~2.0MPa, the mercaptan removal agent is 0.5~10: 1 with the ratio of liquefied petroleum gas (LPG).
6. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: the described mercaptan removal agent aqueous solution contains two kinds of components, and first component concentrations is 0.1wt%~50wt%, and second concentration of component is 0.1wt%~98wt%.
7. the process for purification of liquefied petroleum gas (LPG) according to claim 1, it is characterized in that: the operational condition of the steam stripping regeneration of the described mercaptan removal agent aqueous solution in stripping tower is: 80 ℃~130 ℃ of temperature, pressure 0.1MPa~0.6MPa.
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