CN103965984A - Method for removing mercaptan in liquefied petroleum gas through catalysis - Google Patents
Method for removing mercaptan in liquefied petroleum gas through catalysis Download PDFInfo
- Publication number
- CN103965984A CN103965984A CN201310044941.0A CN201310044941A CN103965984A CN 103965984 A CN103965984 A CN 103965984A CN 201310044941 A CN201310044941 A CN 201310044941A CN 103965984 A CN103965984 A CN 103965984A
- Authority
- CN
- China
- Prior art keywords
- petroleum gas
- liquefied petroleum
- lpg
- mercaptan
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for removing mercaptan in liquefied petroleum gas through catalysis. The method comprises the following steps: mixing liquefied petroleum gas with hydrogen, allowing an obtained mixture to enter a fixed bed reactor and contact with a catalyst in the fixed bed reactor for thiolation and allowing mercaptan in the liquefied petroleum gas to react with active unsaturated hydrocarbon in the liquefied petroleum gas under the action of the catalyst so as to produce a high-boiling point thioether compound, wherein a part of dialkene is selectively saturated and monoolefine is not saturated, so a liquefied petroleum gas mixture is obtained; and allowing the reacted liquefied petroleum gas mixture to enter a distillation column for distillation and separating a liquid petroleum gas fraction from the high-boiling point thioether compound so as to obtain a liquefied petroleum gas product without mercaptan. The method provided by the invention employs the catalytic reaction between raw materials to remove mercaptan without introduction of an auxiliary agent for participation in the reaction, has a high mercaptan removal rate and no discharge of alkaline residue and simplifies conventional process for removal of mercaptan in liquefied petroleum gas.
Description
Technical field
The method and the reaction distillation system that the present invention relates to a kind of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, belong to LPG Desulfurization purification techniques field.
Background technology
Liquefied petroleum gas (LPG) is one of important refinery products, both can be used as efficient clean fuel, can after separating, obtain propylene and C 4 fraction again, as olefinic polymerization raw material and etherificate and raw material for alkylation.But contain hydrogen sulfide, mercaptan sulfides that concentration is higher in liquefied petroleum gas (LPG), these sulfide have caused disadvantageous effect to following process utilization and the environment protection of liquefied petroleum gas (LPG), therefore, liquefied petroleum gas (LPG) is carried out to desulfurization and be very important.
In liquefied petroleum gas (LPG), contained sulfide is mainly hydrogen sulfide, carbonylsulfide and mercaptan.Therefore, conventional LPG Desulfurization system mainly comprises depriving hydrogen sulphide, carbonylsulfide and two parts of mercaptan removal.In concrete sulfur removal technology, liquefied petroleum gas (LPG) is first through alkanolamine solution desulfurization unit, remove most hydrogen sulfide, more further remove remaining hydrogen sulfide by caustic prescrub unit, finally the liquefied petroleum gas (LPG) that contains a certain amount of mercaptan after smart depriving hydrogen sulphide is carried out to mercaptan removal processing.In said process, mercaptan removal is the difficult point place of LPG Desulfurization always, is also the focus of researching and developing both at home and abroad.
1958, company of the U.S. global oil product (UOP) proposed method-Merox extracting and oxidizing method of petroleum gas sweetening the earliest, open in patent US2882224.The ultimate principle of this technology is that the NaOH solution that is dissolved with sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt catalyst is fully mixed in contact tower with liquefied petroleum gas (LPG), mercaptan in liquefied petroleum gas (LPG) is reacted with NaOH generate sodium mercaptides to transfer in alkali lye, the alkali lye that contains sodium mercaptides enters regenerator column, and pass into air, under cobalt sulfonated phthalocyanine effect, sodium mercaptides is oxidized to disulphide, makes alkali lye obtain recycling after regeneration.Its reaction equation is as follows:
RSH+NaOH→RSNa+H
2O
4RSNa+O
2+H
2O→2RSSR+4NaOH
Because this technology is used caustic alkali and catalyzer in a large number, when in liquefied petroleum gas (LPG), mercaptans content is higher, alkali lye needs frequent replacing, not only cause a large amount of alkaline residue discharges, and disulphide in oxidation regeneration agent alkali lye is difficult to be separated, thereby often cause the total sulfur content of the liquefied petroleum gas (LPG) after refining to exceed standard.For the problems referred to above, the improvement that Uop Inc. continues Merox technology, form so far a series of petroleum gas sweetening technique, open in patent US2988500, US 3108081, US 4049572, US 4626341, its general technical progress is to have reduced caustic alkali consumption, and has improved mercaptan removal rate.Milliken Co. (Merichem Co.) has developed fiber-film (Fiber-Film) contactor alkaline purification mercaptan removal technique, open in patent US 4675100, US 4746494, US 4753722, its know-why is identical with Merox technology, but its advantage has been to increase the contact area of alkali lye and liquefied gas, reduce the consumption of caustic alkali, and there is higher extraction efficiency.But these two kinds of technology all consume alkali lye, all cause a large amount of alkaline residue discharges, bring immense pressure to environment.Therefore the method that the method for, developing environmental protection more removes mercaptan in liquefied gas just seems very necessary.
In order to solve alkali lye emission problem, CN1418937A discloses a kind of industrialization liquefied petroleum gas (LPG) process for purification.Liquefied petroleum gas (LPG) after the method adopts the mercaptan-eliminating catalyst being arranged in fixed-bed reactor to smart depriving hydrogen sulphide is carried out mercaptan conversion processing, make mercaptan under the effect of catalyzer, react and generate disulphide with trace oxygen (or artificial appropriate oxygen supplementing) residual in liquefied petroleum gas (LPG), then the liquefied petroleum gas (LPG) that contains disulphide is carried out to rectifying, obtain refining liquefied petroleum gas product in rectifying tower top, at the bottom of rectifying tower, obtain the mixture of enrichment disulphide.The activeconstituents of this mercaptan-eliminating catalyst is iron calcium oxide or hydrated iron calcium oxide.
CN1702157A discloses a kind of method of refining liquefied petrolium gas (LPG).The method is under the condition of complete alkali-free, the liquefied petroleum gas (LPG) after hydramine depriving hydrogen sulphide to be hydrolyzed successively after the sulphuring treatment of decarbonylation base and depriving hydrogen sulphide process, be the liquid oxygenating agent of tertbutyl peroxide to adding active principle in liquefied petroleum gas (LPG) again, make again it carry out mercaptan conversion processing by dual purpose catalyst bed, under dual purpose catalyst effect, tertbutyl peroxide decomposition discharges active oxygen, and mercaptan oxidation is become to disulphide; The active ingredient of dual purpose catalyst is the compound of manganese.Finally, the liquefied petroleum gas (LPG) after transforming thiol treatment is carried out to gas fractionation and rectification process successively, can obtain the last running of refining liquefied petroleum gas (LPG) and enrichment disulphide.
The method of above-mentioned two Patent Application Publications all adopts fixed bed alkali-free catalytic oxidation to transform mercaptan, under the effect of catalyzer, realize the conversion of mercaptan, although these two kinds of methods have been avoided the use of caustic alkali, alleviate to a certain extent environmental protection pressure, transformed but all need extra active oxygen species to participate in mercaptan.At the dissolved oxygen taking in liquefied petroleum gas (LPG) during as oxygen source, due to the content extremely low (general < 50 μ g/g) of dissolved oxygen, and mercaptans content in liquefied petroleum gas (LPG) is generally up to hundreds of μ g/g, so only rely on the amount of dissolved oxygen in liquefied petroleum gas (LPG) can not realize the wherein thorough conversion of mercaptan, and can bring larger operational risk by the appropriate oxygen of artificial introducing.When using tertbutyl peroxide as oxygenating agent, although can be by controlling the more fully mercaptan in conversion fluid liquefied oil gas of addition of oxygenating agent, but the decomposition of tertbutyl peroxide produces isopropylcarbinol, this has brought difficulty with regard to the separation and purification of giving liquefied petroleum gas product, and may cause disadvantageous effect to its further processing and utilization.
In recent years, thioetherification method has been widely used for removing the mercaptan in refinery hydrocarbon fraction, utilizes the reaction between component in raw material to remove mercaptan.Specifically, in some hydrocarbon fraction, contain alkene and the diolefine (as butylene, isoprene etc.) of mercaptan and high reaction activity, thioetherification reaction is, by reacting between mercaptan and active olefin, mercaptan is converted into high boiling thioether, through fractionation, formed high boiling sulfide compound is separated from hydrocarbon-fraction again, and then reached the object that removes mercaptan from raw material.The existing numerous patent report of the thioetherification technology of hydro carbons at present.For example, patent US 5851383 discloses a kind of light olefin mercaptan removal and process for selective hydrogenation, the C that this technique produces catalytic cracking unit
3-C
5cut and hydrogen are mixed into fixed-bed reactor, and under thioetherification catalyst effect, the diene in distillate and thiol reactant generate high boiling thioether, unnecessary diene by selectivity hydrogenation saturated be monoene; Reaction product imports distillation tower and carries out fractionation, and the light constituent that removes mercaptan flows out from tower top, and thioether and heavy constituent be enrichment discharge at the bottom of tower.In specific embodiment, the catalyzer adopting in fixed-bed reactor is that the Ni taking aluminum oxide as carrier is catalyst based, and it can realize the thioetherification reaction of mercaptan and the selective hydrogenation of diene.Thioetherification reaction temperature is 125 DEG C, and pressure is 4100kPa.The disclosed thioetherification reaction excess Temperature of this patent, causes the saturated and isomerization of part monoolefin hydrogenation, and alkene utilization ratio is low, and major part does not participate in thioetherification reaction and goes.
Patent US 7638041 discloses a kind of technique of the FCC of processing petroleum naphtha, and it comprises the thioetherification mercaptan removal of light naphtha fraction, the selective hydrogenation of middle runnings.Full cut catalytic cracking petroleum naphtha and hydrogen are mixed into distillation tower, and are split into light component (LCN), intermediate component (MCN) and heavy component (HCN).The rectifying section of distillation tower is equipped with thioetherification catalyst, and here the diolefine in LCN and mercaptan react and forms high boiling point thioether, and enter stripping section by distillation, at the bottom of tower, are concentrated.LCN after mercaptan removal discharges from tower top.MCN enters side stripper tower with side stream, the in-built selective hydrogenation catalyst of tower, lighting end in MCN enters front end distillation tower from side line top of tower, simultaneously, selective hydrogenation of dienes in MCN is monoene, and product is discharged or mixes discharge with the HCN including sulfocompound of distillation tower bottom at the bottom of tower.Wherein, thioetherification reaction catalyzer used is that loading type Ni is catalyst based.Selective hydrogenation unit catalyzer used is loaded palladium catalyst.Processing condition and the case study on implementation of the not mentioned thioetherification reaction that can be for reference of this patent.
Patent US20100059413 discloses a kind of for remove the thioetherification technique of mercaptan from gas fraction.In specific embodiment, in feed gas, contain the sulphur impurities such as hydro carbons and sulfur alcohol such as alkene, diolefine and alkynes.Unstripped gas keeps gas phase and hydrogen to be mixed into thioetherification reaction device, under the effect of catalyzer, mercaptan and active olefin react and generate high boiling point thioether, reaction product passes into separation column and separates, do not discharge from tower top containing the gas fraction of mercaptan, heavy constituent thioether obtains enrichment and discharges at the bottom of tower.The thioetherification catalyst that this technique adopts is that thioetherification reaction temperature is 176 °F containing the catalyzer of palladium, silver-colored isoreactivity metal, and reaction pressure is 150psig.But this patent does not relate to more information about thioetherification catalyst aspect.
Above-mentioned patent is all the technology transforming for the mercaptan in petroleum liquid hydro carbons cut, and does not relate to removing of mercaptan sulfocompound in liquefied petroleum gas (LPG), and above-mentioned patent does not relate to the case study on implementation of the thiomethyl alcohol thioetherification reaction in liquefied petroleum gas (LPG).
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, it is the method for liquefied petroleum gas (LPG) mercaptan is transformed of a kind of non-alkali liquor discharge, have temperature of reaction low, can not cause active ethylenic unsaturation polymerized hydrocarbon and the feature that monoene hydrogenation is saturated and mercaptan transformation efficiency is higher.
For achieving the above object, the invention provides a kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, it comprises the following steps:
After being mixed with hydrogen, the liquefied petroleum gas (LPG) that contains mercaptan and unsaturated hydrocarbons enters a fixed-bed reactor top, liquefied petroleum gas (LPG) after the mixed hydrogen beds loading in reactor of flowing through from top to bottom in reactor, contact and carry out thioetherification reaction with the catalyzer wherein loading, make lower boiling mercaptan in liquefied petroleum gas (LPG) under the effect of catalyzer with liquefied petroleum gas (LPG) in active unsaturated hydrocarbons (as iso-butylene, divinyl etc.) reaction changes into high boiling sulfide compound, and it is saturated that part diolefine obtains selectivity, and wherein contained monoolefine not by saturated, obtain liquefied petroleum gas (LPG) gas mixture.
Reacted liquefied petroleum gas (LPG) gas mixture enters a distillation tower from reactor bottom outflow and distills processing, liquid petroleum gas cut is separated with high boiling point sulfide compound, the liquid petroleum gas cut removing after mercaptan flows out from tower top, and the high boiling point sulfide compound forming goes out from tower bottom flow.
In aforesaid method, after distillation is processed, do not contain mercaptan or the lower boiling C containing denier mercaptan
3-C
4hydrocarbon component, in tower top enrichment, flows out and obtains clean liquefied petroleum gas product from tower top, can be used as clean fuel or etherificate, raw material for alkylation; And the enrichment at the bottom of tower of the liquefied gas of high boiling point thioether and other heavy constituents, go out from tower bottom flow, can be mixed into selectivity gasoline hydrodesulfurizationmethod unit with catalytic cracking heavy petrol and obtain clean gasoline blend component by hydrogenating desulfurization, or obtain high added value fine chemical product by further processing.
In aforesaid method provided by the invention, preferably, the raw liquefied petroleum gas that enters fixed-bed reactor is that its contained sulfide is mainly thiomethyl alcohol through removing hydrogen sulfide and carbonylsulfide liquefied petroleum gas (LPG) after treatment, and active unsaturated hydrocarbons is mainly iso-butylene and divinyl.Hydrogen sulfide and carbonylsulfide contained in liquefied petroleum gas (LPG) are extremely micro-, and contained sulfide is mainly lightweight mercaptan (as thiomethyl alcohol and sulfur alcohol), and taking thiomethyl alcohol as main.The hydrocarbon composition of stock liquid liquefied oil gas is mainly C
3-C
4cut, the unsaturated hydrocarbons compounds wherein containing has: propylene, 1-butylene, 2-butylene, iso-butylene, 1,3-butadiene etc.Usually, concentrations of mercaptans contained in charging liquefied gas is higher than 50 μ g/g, and concentrations of mercaptans can be up to 1000 μ g/g sometimes.
In aforesaid method provided by the present invention, preferably, liquefied petroleum gas (LPG) is to contact with catalyzer with the form of liquid phase.
In aforesaid method provided by the present invention, preferably, liquefied petroleum gas (LPG) and hydrogen enter fixed-bed reactor from top, and it is saturated that the object that passes into hydrogen is to make the divinyl in liquefied petroleum gas (LPG) to be able to, and be beneficial to the activity that maintains catalyzer.
Provided by the present invention above-mentioned in, in reaction process, pass into hydrogen and maintain certain pressure main purpose be make liquefied petroleum gas (LPG) in reaction for liquid phase, to increase the flux of reactor; In addition, hydrogen plays certain provide protection to catalyzer, reduces alkene and forms carbon distribution in catalyst surface generation polymerization.
In aforesaid method provided by the present invention, preferably, the catalyzer adopting is to make mercaptan be converted into the thioetherification catalyst of thioether; More preferably, the active ingredient of described thioetherification catalyst is one or both in transiting metal nickel, molybdenum, tungsten, active ingredient, taking metal salt solution as presoma, adopts equi-volume impregnating or step impregnation method to load on carrier, and the carrier of described thioetherification catalyst is γ-Al
2o
3, SiO
2-Al
2o
3with one or more the combination in spinel.Thioetherification catalyst of the present invention also can adopt thioetherification catalyst of the prior art, for example: and published mercaptan transfer catalyst in CN101885985A, CN102423718A, CN102416344A, but be not limited to these catalyzer.
According to specific embodiment of the invention scheme, preferably, in the gross weight of catalyzer, this catalyzer contains NiO6-20wt%, MoO
35-14wt%, surplus is oxide carrier; Or in the gross weight of catalyzer, this catalyzer contains NiO 7-18wt%, WO
34-13wt%, surplus is oxide carrier.
According to specific embodiment of the invention scheme, preferably, the external shape of thioetherification catalyst of the present invention is spherical, column or trifolium shape, and its specific surface area is 60-300m
2/ g, pore volume is 0.3-1.0cm
3/ g, tap density is 0.5-1.0g/cm
3.
Thioetherification catalyst of the present invention needs to adopt conventional vulcanization to carry out prevulcanized before use, so that metal oxide active precursor is converted into the active phase of sulfide with catalytic activity; The prevulcanized of catalyzer can be by two kinds of modes of the outer sulfuration of sulfuration and device in device, and vulcanizing agent can be selected the sulfur compounds such as Methyl disulfide, hydrogen sulfide, dithiocarbonic anhydride.Under the effect of this catalyzer, the active unsaturated hydrocarbons generation electrophilic addition reaction in mercaptan and liquefied petroleum gas (LPG), generates high boiling sulfide compound.
In aforesaid method provided by the invention, preferably, thioetherification reaction is carried out in fixed-bed reactor, and temperature of reaction is 40-180 DEG C, reaction pressure be 0.8-4.0MPa (gauge pressure, lower with, be preferably 1.0-2.4MPa), liquid phase volume air speed is 1-10h
-1(be preferably 1.5-3.0h
-1), the volume ratio of hydrogen and liquefied petroleum gas (LPG) is 0-15 (being preferably 3-10).
In aforesaid method provided by the invention, preferably, distillation adopts common distillation tower to carry out, liquid petroleum gas cut is separated with high boiling point sulfide compound, reacted liquefied petroleum gas (LPG) gas mixture enters distillation tower from the middle part of tower, the tower top temperature of distillation tower is 45-80 DEG C, and column bottom temperature is 65-150 DEG C; The working pressure of distillation tower is 0.4-2.2MPa, and reflux ratio is 2-7, and reflux temperature is 25-50 DEG C.After separating, what flow out from distillation tower tower top is refining liquefied petrolium gas (LPG) cut, and its contained concentrations of mercaptans is not all 1-20 μ g/g depending on operational condition, and what tower bottom flow went out is the mixture that contains sulfide compound and part hydro carbons heavy constituent.
Compared with traditional catalytic oxidation desulfurization alcohol technology, liquefied petroleum gas mercaptan removal technique provided by the invention takes full advantage of the catalyzed reaction between component in raw material and removes mercaptan, participate in reaction without introduce auxiliary agent in raw material, not only there is higher mercaptan decreasing ratio, thereby discharge without alkaline residue, and can realize the comprehensive utilization of mercaptan converted product, there is good economic and social benefit.In addition, the present invention is also different from the thioetherification mercaptan removal technique of existing other petroleum hydrocarbon cuts, and the raw material adopting contains abundant monoolefine, and diene content is few, transform but still can realize mercaptan sulfur etherificate more completely, and catalyzer used is non-precious metal catalyst.In method provided by the present invention, thioetherification reaction temperature is lower, can not cause isomery and the polymerization of active unsaturated hydrocarbons.
Brief description of the drawings
The process flow diagram of the method for the liquefied petroleum gas (LPG) catalytic desulfurization alcohol that Fig. 1 provides for embodiment 1;
Fig. 2 is mercaptan decreasing ratio relation curve over time in liquefied petroleum gas (LPG).
Main drawing reference numeral explanation:
1 head tank 2 surge tank 3 fresh feed pump 4 Hydrogen Line 5 fixed-bed reactor 6 holding tank 7 distillation tower 8 condenser 9 return tank 10 reboilers
Embodiment
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
The present embodiment provides a kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, its technical process as shown in Figure 1, for raw liquefied petroleum gas for through depriving hydrogen sulphide, carbonylsulfide liquefied petroleum gas (LPG) after treatment, its composition is as shown in table 1.
Table 1
| Composition | Content |
| Propane, % (v/v) | 9.3 |
| Propylene, % (v/v) | 31.46 |
| Normal butane, % (v/v) | 5.66 |
| Trimethylmethane, % (v/v) | 25.07 |
| 1-butylene, % (v/v) | 6.57 |
| Iso-butylene, % (v/v) | 8.71 |
| Cis-2-butene, % (v/v) | 5.36 |
| Trans-2-butene, % (v/v) | 7.83 |
| 1,3-butadiene, % (v/v) | 0.03 |
| Thiomethyl alcohol, μ g/g | 276.6 |
| Hydrogen sulfide, μ g/g | 7.4 |
The method of the liquefied petroleum gas (LPG) catalytic desulfurization alcohol that the present embodiment provides comprises the following steps:
Raw liquefied petroleum gas enters surge tank 2 by head tank 1, passes into H
2in 1.0MPa left and right, make raw liquefied petroleum gas remain liquid phase pressure-controlling;
By fresh feed pump 3, raw liquefied petroleum gas is carried, raw liquefied petroleum gas is together sent in fixed-bed reactor 5 after first mixing with from the hydrogen of Hydrogen Line 4, contact and react with thioetherification catalyst, reacted liquefied petroleum gas (LPG) gas mixture is discharged from reactor 5 bottoms, enters among holding tank 6;
In holding tank 6, H
2discharge from holding tank 6 tops, liquefied petroleum gas (LPG) gas mixture is discharged from holding tank 6 bottoms, enters distillation tower 7 from the middle part of distillation tower 7;
Reacted liquefied petroleum gas (LPG) gas mixture in distillation tower 7 through distillation process after, what flow out from the return tank 9 at distillation tower 7 tops is the liquefied petroleum gas product of super low sulfur, what flow out from tower bottom is the mixture of high boiling sulfocompound and part hydro carbons heavy constituent, and the part mixture of discharging at the bottom of tower can return to distillation tower after reboiler 10 vaporizations.
In the present embodiment, wherein, thioetherification reaction is carried out in fixed-bed reactor 5, and the thioetherification catalyst loadings in reactor 5 is 7.5mL, and when catalyst loading, fill with quartz sand at beds two ends, and this thioetherification catalyst is Ni-Mo/SiO
2-Al
2o
3system Catalyst, with SiO
2and Al
2o
3composite oxides be carrier, compound loaded to carrier by step impregnation method by transiting metal nickel, molybdenum; In total catalyst weight, the composition content of catalyzer is: NiO 17wt%, MoO
35wt%, SiO
2-Al
2o
3(containing Al
2o
387wt%, SiO
213wt%) 78wt%, catalyst grain size is 20-40 order;
Wherein, the temperature of reaction in fixed-bed reactor 5 is 90 DEG C, and reaction pressure is 2.5MPa, and liquid phase volume air speed is 4h
-1, the volume ratio of hydrogen and liquefied petroleum gas (LPG) is 6;
Wherein, the tower top of distillation tower 7 and column bottom temperature are controlled respectively as approximately 50 DEG C and 110 DEG C, and the control of distillation tower working pressure is about 0.8MPa, and trim the top of column is than being 2-7, and reflux temperature is 25-50 DEG C.
The liquefied petroleum gas product flowing out to stock liquid liquefied oil gas with from distillation tower 7 evaporator overhead condensers 8 every 4 hours gathers liquid phase sample with liquefied gas sampling thief, adopt high-pressure liquid phase sampler sample introduction, analyze hydrocarbon composition and thiomethyl alcohol content wherein, adopt gas chromatograph flame ionization ditector (GC-FID) to detect the hydrocarbon composition content of liquefied petroleum gas (LPG), adopt gas chromatograph sulphur matter chemiluminescence detector (GC-SCD) to detect thiomethyl alcohol content, according to thiomethyl alcohol content in the liquefied petroleum gas product at different time interval, calculate mercaptan decreasing ratio in the liquefied petroleum gas (LPG) of different time, and draw mercaptan decreasing ratio relation curve over time in liquefied petroleum gas (LPG), result as shown in Figure 2.
As can be seen from Figure 2, react under these conditions after 100h, after testing, from the liquefied petroleum gas product out of distillation tower 7 tops, thiomethyl alcohol content is 11.2 μ g/g, and its mercaptan decreasing ratio reaches 96.0%.
Embodiment 2
The present embodiment provides a kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, the operation steps of itself and embodiment 1 is basic identical, raw materials used, loaded catalyst, generation are dredged the fixed-bed reactor operational condition of etherification reaction and reacted liquefied petroleum gas (LPG) gas mixture are carried out to the distillation tower operational condition of fractionation processing identical with embodiment 1, and thioetherification catalyst still adopts Ni-Mo/SiO
2-Al
2o
3system Catalyst, difference is the levels of transition metals difference of catalyzer.At the present embodiment Ni-Mo/SiO used
2-Al
2o
3in System Catalyst, in total catalyst weight, the composition content of catalyzer is: NiO 12.5wt%, MoO
38.5wt%, SiO
2-Al
2o
3(containing Al
2o
387wt%, SiO
213wt%) 79wt%.
As can be seen from Figure 2, reaction continues after 100h, and recording thiomethyl alcohol content in the liquefied petroleum gas product after distillation tower top mercaptan removal is 5.0 μ g/g, and its desulfurization degree reaches 98.2%.
Embodiment 3
The present embodiment provides a kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol, the operation steps of itself and embodiment 1 is basic identical, used catalyst loadings is identical with embodiment 1, and difference is: raw liquefied petroleum gas composition used is different with thiomethyl alcohol sulphur content, and raw material composition is as shown in table 2; Thioetherification catalyst is Ni-W/SiO
2-Al
2o
3system Catalyst, compound loaded to carrier by step impregnation method by transiting metal nickel, tungsten, in total catalyst weight, the composition content of catalyzer is: NiO 12wt%, WO
38wt%, SiO
2-Al
2o
3composite oxides are (containing Al
2o
387wt%, SiO
213wt%) 80wt%; Temperature of reaction is 80 DEG C, and reaction pressure is 2.0MPa, and liquid phase volume air speed is 2.5h
-1, the volume ratio of hydrogen and liquefied petroleum gas (LPG) is 4.The operational condition of distillation tower is: tower top and column bottom temperature are about respectively 65 DEG C and 145 DEG C, and distillation tower working pressure is about 1.2MPa.
Table 2
| Composition | Content |
| Propane, % (v/v) | 6.89 |
| Propylene, % (v/v) | 25.95 |
| Normal butane, % (v/v) | 6.43 |
| Trimethylmethane, % (v/v) | 24.29 |
| 1-butylene, % (v/v) | 7.74 |
| Iso-butylene, % (v/v) | 10.57 |
| Cis-2-butene, % (v/v) | 7.38 |
| Trans-2-butene, % (v/v) | 10.72 |
| 1,3-butadiene, % (v/v) | 0.04 |
| Thiomethyl alcohol, μ g/g | 414.9 |
| Hydrogen sulfide, μ g/g | 8.2 |
As can be seen from Figure 2, process after 100h, the liquid petroleum gas cut after the piptonychia mercaptan that distillation tower evaporator overhead condenser is flowed out carries out analysis of sulfur content, obtains wherein thiomethyl alcohol content and is reduced to 10.4 μ g/g, and its mercaptan decreasing ratio reaches 97.5%.
Claims (10)
1. a method for liquefied petroleum gas (LPG) catalytic desulfurization alcohol, it comprises the following steps:
After being mixed with hydrogen, the liquefied petroleum gas (LPG) that contains mercaptan and unsaturated hydrocarbons enters fixed-bed reactor, contact and carry out thioetherification reaction with the catalyzer wherein loading, make the mercaptan in liquefied petroleum gas (LPG) react and change into high boiling sulfide compound with the active unsaturated hydrocarbons in liquefied petroleum gas (LPG) under the effect of catalyzer, and it is saturated that part diolefine obtains selectivity, and wherein contained monoolefine, not by saturated, obtains liquefied petroleum gas (LPG) gas mixture;
Reacted liquefied petroleum gas (LPG) gas mixture enters a distillation tower and distills processing, liquid petroleum gas cut is separated with high boiling point sulfide compound, the liquid petroleum gas cut removing after mercaptan flows out from tower top, and the high boiling point sulfide compound forming goes out from tower bottom flow.
2. method according to claim 1, wherein, described liquefied petroleum gas (LPG) is that its contained sulfide is mainly thiomethyl alcohol through removing hydrogen sulfide and carbonylsulfide liquefied petroleum gas (LPG) after treatment, active unsaturated hydrocarbons is mainly iso-butylene and divinyl.
3. method according to claim 2, wherein, described liquefied petroleum gas (LPG) is to contact with catalyzer with the form of liquid phase.
4. method according to claim 1, wherein, described liquefied petroleum gas (LPG) and hydrogen enter fixed-bed reactor from top.
5. method according to claim 1, wherein, described catalyzer is to make mercaptan be converted into the thioetherification catalyst of thioether.
6. method according to claim 5, wherein, the active ingredient of described thioetherification catalyst is one or both in nickel, molybdenum, tungsten, the carrier of described thioetherification catalyst is γ-Al
2o
3, SiO
2-Al
2o
3the combination of one or more in composite oxides and spinel.
7. method according to claim 1 or 5, wherein, in the gross weight of described catalyzer, described catalyzer contains NiO 6-20wt%, MoO
35-14wt%, surplus is oxide carrier;
Or in the gross weight of described catalyzer, described catalyzer contains NiO 7-18wt%, WO
34-13wt%, surplus is oxide carrier.
8. according to the method described in claim 5-7 any one, wherein, being shaped as of described thioetherification catalyst is spherical, column or trifolium shape, and its specific surface area is 60-300m
2/ g, pore volume is 0.3-1.0cm
3/ g, tap density is 0.5-1.0g/cm
3, this catalyzer carries out prevulcanized before use.
9. method according to claim 1, wherein, described thioetherification reaction is carried out in fixed-bed reactor, and temperature of reaction is 40-180 DEG C, and reaction pressure is 0.8-4.0MPa, and liquid phase volume air speed is 1-10h
-1, the volume ratio of hydrogen and liquefied petroleum gas (LPG) is 0-15.
10. method according to claim 1, wherein, described distillation adopts distillation tower to carry out, and reacted liquefied petroleum gas (LPG) gas mixture enters distillation tower from the middle part of tower, and the tower top temperature of distillation tower is 45-80 DEG C, and column bottom temperature is 65-150 DEG C; The working pressure of distillation tower is 0.4-2.2MPa, and reflux ratio is 2-7, and reflux temperature is 25-50 DEG C; After separating, what go out from tower bottom flow is the mixture that contains sulfide compound and part hydro carbons heavy constituent, and what tower top flowed out is refining liquefied petrolium gas (LPG) cut.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310044941.0A CN103965984B (en) | 2013-02-04 | 2013-02-04 | A kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310044941.0A CN103965984B (en) | 2013-02-04 | 2013-02-04 | A kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965984A true CN103965984A (en) | 2014-08-06 |
| CN103965984B CN103965984B (en) | 2015-09-23 |
Family
ID=51235994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310044941.0A Active CN103965984B (en) | 2013-02-04 | 2013-02-04 | A kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965984B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176615A (en) * | 2014-06-05 | 2015-12-23 | 中国石油化工股份有限公司 | Liquefied gas fixed bed mercaptan removal method |
| CN106179354A (en) * | 2016-07-15 | 2016-12-07 | 北京恩泽福莱科技有限公司 | A kind of mercaptan etherification catalyst and preparation method and application |
| CN106554839A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | The method for removing hydrogen sulfide and mercaptan in liquefied petroleum gas using fixed bed reactors simultaneously |
| CN108205041A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for analyzing sulfur-containing compounds in liquefied gas |
| CN109725065A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The analysis method of sulfur alcohol compound in a kind of light oil |
| CN111748374A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
| CN111748375A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| EP3882329A1 (en) | 2020-03-18 | 2021-09-22 | Indian Oil Corporation Limited | Process for removal of sulfur and other impurities from olefinic liquefied petroleum gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474574A (en) * | 2008-10-24 | 2009-07-08 | 长春工业大学 | Solid catalyst for petroleum liquid component sweetening and preparation method |
| CN101993750A (en) * | 2010-11-29 | 2011-03-30 | 中国石油大学(北京) | Method for refining liquefied petroleum gas |
-
2013
- 2013-02-04 CN CN201310044941.0A patent/CN103965984B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474574A (en) * | 2008-10-24 | 2009-07-08 | 长春工业大学 | Solid catalyst for petroleum liquid component sweetening and preparation method |
| CN101993750A (en) * | 2010-11-29 | 2011-03-30 | 中国石油大学(北京) | Method for refining liquefied petroleum gas |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176615A (en) * | 2014-06-05 | 2015-12-23 | 中国石油化工股份有限公司 | Liquefied gas fixed bed mercaptan removal method |
| CN106554839A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | The method for removing hydrogen sulfide and mercaptan in liquefied petroleum gas using fixed bed reactors simultaneously |
| CN106179354A (en) * | 2016-07-15 | 2016-12-07 | 北京恩泽福莱科技有限公司 | A kind of mercaptan etherification catalyst and preparation method and application |
| CN106179354B (en) * | 2016-07-15 | 2019-01-08 | 北京恩泽福莱科技有限公司 | A kind of mercaptan etherification catalyst and the preparation method and application thereof |
| CN108205041A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for analyzing sulfur-containing compounds in liquefied gas |
| CN109725065A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The analysis method of sulfur alcohol compound in a kind of light oil |
| CN111748374A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
| CN111748375A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| CN111748375B (en) * | 2019-03-28 | 2021-12-17 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| CN111748374B (en) * | 2019-03-28 | 2021-12-17 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
| EP3882329A1 (en) | 2020-03-18 | 2021-09-22 | Indian Oil Corporation Limited | Process for removal of sulfur and other impurities from olefinic liquefied petroleum gas |
| US11739277B2 (en) | 2020-03-18 | 2023-08-29 | Indian Oil Corporation Limited | Process for removal of sulfur and other impurities from olefinic liquefied petroleum gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965984B (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103965984B (en) | A kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol | |
| CN101787307B (en) | Gasoline hydrodesulfurization method | |
| CN104479738B (en) | A kind of Deep Desulfurization of FCC Gasoline combination process | |
| CN101492608A (en) | Method for deep desulfurization olefin hydrocarbon reduction of inferior gasoline | |
| CN103992832B (en) | A kind of process for purification of liquefied petroleum gas | |
| CN103289740A (en) | Method for preparing clean fuel oil from coal tar | |
| CN101492609A (en) | Method for deep desulfurization olefin hydrocarbon reduction of gasoline | |
| CN103911177A (en) | Deep desulfurization method for saturated liquid hydrocarbon | |
| CN102399585A (en) | Method for producing sweet gasoline | |
| CN106147844A (en) | A kind of method of hydrotreating producing super low-sulfur oil | |
| KR20150071665A (en) | Process for the hydrodesulphurization of hydrocarbon cuts | |
| CN102451693B (en) | Hydrogenation mercaptan-removal catalyst and preparation method and use thereof | |
| CN101089129B (en) | Process of selectively hydrogenating and desulfurizing inferior gasoline | |
| CN107353934B (en) | Method for reducing octane number loss of gasoline of S Zorb device | |
| CN103059964B (en) | Method for producing ultra-low sulfur gasoline | |
| CN101362671B (en) | Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery | |
| CN101492610A (en) | Method for deep desulfurization olefin hydrocarbon reduction of gasoline | |
| CN103396832A (en) | Modification method for full-range catalytic cracking gasoline | |
| CN103740407B (en) | Alkali cleaning-extraction-washing-hydrogenation combined process for producing low-sulfur-content gasoline | |
| CN103740405B (en) | Alkali cleaning-extraction-hydrogenation combined process for producing low-sulfur-content gasoline | |
| CN103059947B (en) | Method for production of super-clean gasoline from inferior gasoline | |
| CN103059951B (en) | Catalytic cracking and catalytic gasoline hydrogenation combined technological method | |
| CN102453532B (en) | Method for producing low-sulfur gasoline | |
| CN104178218B (en) | A kind of liquefied gas and FCC gasoline combination sulfur removal technology | |
| CN114763493B (en) | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |