CN107201254A - A kind of desulfurization refining method of mixed liquefied oil gas - Google Patents

A kind of desulfurization refining method of mixed liquefied oil gas Download PDF

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Publication number
CN107201254A
CN107201254A CN201610150711.6A CN201610150711A CN107201254A CN 107201254 A CN107201254 A CN 107201254A CN 201610150711 A CN201610150711 A CN 201610150711A CN 107201254 A CN107201254 A CN 107201254A
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CN
China
Prior art keywords
liquefied petroleum
petroleum gas
catalytic cracking
gas
coking
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CN201610150711.6A
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CN107201254B (en
Inventor
潘光成
赵杰
李涛
赵丽萍
常春艳
吴明清
陶志平
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/048—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by liquid-liquid extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention provides a kind of process for purification of mixed liquefied oil gas.The process for purification that the present invention is provided is that the riser reactor that the coking liquefied petroleum gas from coking plant is passed through into catalytic cracking unit carries out cracking reaction together with catalytic cracking feeds, then distillated from the fractionating system in catalytic cracking unit as the mixed liquefied oil gas for being mixed with catalytic liquefied petroleum gas, it is then fed into vulcanization hydrogen extraction unit and removes hydrogen sulfide and mercaptan respectively with mercaptan extraction device, the liquefied petroleum gas product sulfur content after desulfurization is not more than 10 μ g/g.Mixed liquefied oil gas after refined can fractionate out the propylene product for meeting sulfur content requirement, and can be used as the MTBE of production low-sulfur raw material.

Description

A kind of desulfurization refining method of mixed liquefied oil gas
Technical field
The invention belongs to the field of refinement of hydrocarbon material.
Background technology
Liquefied petroleum gas (liquefied petroleum gas, LPG) is a kind of important petroleum refining production Product, in refinery mainly including the catalytic liquefied petroleum gas from catalytic cracking unit and from coking plant Coking liquefied petroleum gas, and the mixture being mainly made up of the hydrocarbon of carbon three and C_4 hydrocarbon.Liquefied petroleum gas Purposes includes using as civilian or vehicle fuel, and is used as industrial chemicals, such as extraction The raw material of commodity propylene and the methyl tertiary butyl ether(MTBE) (MTBE) of synthetic gasoline anti-knock agent is used.Liquefy stone Oil gas is usually required can be as purpose product by desulfuration purification.
Unpurified liquefied petroleum gas contains harmful sulfide, and the sulfide is main with hydrogen sulfide and sulphur Based on alcohol, and mercaptan is based on methyl mercaptan, other a small amount of sulfide include cos (COS) with Thioether etc..Comparatively, the sulfide in coking liquefied petroleum gas is compared with the vulcanization in catalytic liquefied petroleum gas Thing is more more complicated, also some higher in content, is especially that non-mercaptan sulfur proportion is very big, in addition burnt Change liquefied petroleum gas be easily carried from coking plant come coke powder, the amount of contained unstable alkadienes with The amount of relatively heavy hydrocarbon component is also some more compared with catalytic liquefied petroleum gas, therefore coking liquefied petroleum gas It is much more difficult compared with catalytic liquefied petroleum gas when carrying out desulfuration purification.
Current LPG Desulfurization indudstrialized refining method mainly includes for the purpose of removing hydrogen sulfide Hydrogen sulfide extracts the continuous process with the mercaptan extracting for the purpose of removing mercaptan.Hydrogen sulfide extracting to be used Hydramine extracts mode, and mercaptan extracting uses caustic extraction mode.The hydramine extracting is with alcamines Solution is contacted compound (such as methyl diethanolamine, MDEA) with liquefied gas, and is absorbed in liquefied gas Hydrogen sulfide, absorb hydrogen sulfide after alkanolamine solution handled through desorption after continuously use.The caustic extraction It is that the liquefied gas extracted with inorganic alkali lye and hydramine after removing hydrogen sulfide is contacted, and absorbs in liquefied gas Mercaptan, absorbs the alkali lye after mercaptan and is used by regeneration treatment Posterior circle.After removing hydrogen sulfide and mercaptan Liquefied petroleum gas turn into purified product.
In order to be met sulfur content requirement alkene (such as propylene, to produce polypropylene, generally will Seek its sulfur content no more than 3mg/m3) and synthesize the MTBE of low sulfur content (in the gasoline standard of state five Under, usually require that MTBE sulfur content is not more than 10 μ g/g), refinery typically requires the liquefaction after refining It is even lower that oil gas sulfur content is not more than 10 μ g/g.And for high sulfur content and containing a large amount of non- Reach that the requirement of such low sulfur content is difficult for the coking liquefied petroleum gas of mercaptan sulfur, after not only refining, Even production meets sulfur content no more than 343mg/m3Requirement civil LPG product also more It is difficult.Therefore, refinery is general separately to carry out desulfurization essence by coking liquefied petroleum gas and catalytic liquefied petroleum gas System, and generally will it is refined after catalytic liquefied petroleum gas carry out gas fractionation processing, concentrate propylene, will point The liquefied petroleum gas of light dydrocarbon hydrocarbon is separated out as synthesis MTBE raw material uses (extraction isobutyl olefinic constituent, with Methanol etherification generates MTBE), and the coking liquefied petroleum gas after refining only is used as the civilian combustion of blending Material is used.In this way, the alkene (propylene and isobutene) in coking liquefied petroleum gas fails to obtain preferably Utilize.
In refinery, also have by coking liquefied petroleum gas and catalytic liquefied petroleum gas merge progress it is above-mentioned Outstanding problem in continuous two steps desulfuration purification, but operation is present in coking liquefied petroleum gas Non- mercaptan sulfur is difficult to remove so that the product sulfur content after refined is still of a relatively high, and its result is likely to Refined products are only used as domestic fuel, its alkene resource is difficult to effective utilization, and hydramine extracting is single First hydramine consumption is very serious with caustic extraction unit alkali lye consumption, and running cost seems higher.
In the prior art, it is main to liquefied petroleum gas Thiolex process generally by the way of caustic extraction Three steps are put forward including caustic extraction, oxidation, back suction, the caustic extraction step refers to the stone that liquefies Oil gas is contacted with alkali lye, the mercaptan in liquefied petroleum gas is transferred in alkali lye, the alkali liquor oxidized step Refer to that the mercaptan oxidation for alkali lye being absorbed under the conditions of catalysis oxidation is disulphide, the back suction puies forward step Suddenly refer to separate the alkali lye after oxidation and disulphide by way of organic solvent back suction is carried, such as This alkali lye is recycled.Many hydrocarbon ils using low-sulfur generally are carried as solvent to the back suction of disulphide, Such as the naphtha after hydrogenation, gasoline, light diesel fuel, back suction extraction solvent passes through hydrogenation again after use Mode is handled.This is unfavorable for without hydrogen source or the not enough refinery of hydrogen source.And naphtha, vapour Oil, light diesel fuel etc. usually contain a certain amount of aromatic hydrocarbons, and even arene content is very high sometimes, when being used as back suction Extraction solvent is unfavorable for hydrocarbon phase and alkali phase in use, easily produce certain emulsion with the alkali lye of contact Separation, and then influence liquefied petroleum gas alkali density desulfurization effect.
Comprehensive existing literature can be seen that when treat sulfide that refined hydrocarbon material contains high content or Non- mercaptan sulfur compound occupies larger ratio (these non-mercaptan sulfur compounds hardly possiblies in contained sulfide With by caustic extraction) when, it is generally difficult to obtain the effect of deep desulfuration using conventional caustic extraction technology.
The content of the invention
It is an object of the invention to overcome the disadvantages mentioned above of prior art to include coking there is provided one kind to liquefy stone The desulfurization refining method that oil gas is mixed with catalytic liquefied petroleum gas, so that mixed liquefied after refined Oil gas sulfur content is not more than 10 μ g/g.
The process for purification includes following continuous step：
(1) the coking liquefied petroleum gas from coking plant is passed through to the catalytic cracking of catalytic cracking unit Riser reactor, occurs cracking reaction together with entering the catalytically cracked material in catalytic cracking riser, The hydrocarbon component of relative macromolecular in coking liquefied petroleum gas changes into relative small molecule respectively with sulfide Hydro carbons and sulfide；
(2) occur the coking liquefied petroleum gas of cracking reaction and urging by catalytically cracked material cracking Change liquefied petroleum gas to flow out together from the fractionating system of catalytic cracking unit, enter the extracting of hydrogen sulfide extraction unit Hydrogen sulfide is removed, mercaptan extraction unit removing mercaptan is then flowed into, the mixed liquefied gas after desulfurization turns into low The liquefied petroleum gas product of sulphur, sulfur content is not more than 10 μ g/g.
Wherein, the coking liquefied petroleum gas from coking plant is to be injected to catalytic cracking reaction by nozzle In device.
Wherein, the hydrogen sulfide extraction unit is preferred to use hydramine extracting mode, including hydramine extracting and alcohol Amine desorption process.
Wherein, mercaptan extraction unit uses caustic extraction mode, including caustic extraction, alkali liquor oxidized and anti- Extract three processes.Wherein caustic extraction, alkali liquor oxidized process can be handled according to prior art.According to this Inventive method, during back suction is carried, back suction extraction solvent can use the hydrocarbon ils of low-sulfur, such as stone after being hydrogenated with Cerebrol, gasoline, light diesel fuel etc., back suction extraction solvent are handled by way of hydrogenation again after use.It is preferred that Mixed liquefied oil gas after desulfurization is separated to a part as the back suction extraction solvent of anti-extractive process, passed through Back suction is again returned at catalytic cracking riser reactor after carrying the disulphide in removing regeneration alkali lye Reason.
Wherein, process for purification of the present invention also includes entering water-filling to the mixed liquefied oil gas after desulfurization Wash and handled with coalescence, then as product.
In the present invention, if not otherwise indicated, the catalytic cracking process, hydramine extractive process, Hydramine desorption process, caustic extraction process, alkali liquor oxidized and anti-extractive process and washing and coalescence are handled Process is carried out using known mode, and the operating condition of each correlated process keeps constant.
The present invention carries out cracking reaction by the way that coking liquefied petroleum gas is passed into catalytic cracking unit, makes The hydrocarbon component and sulfide for obtaining the relative macromolecular in coking liquefied petroleum gas change into relatively small point respectively The hydro carbons and sulfide of son, while entrained non-volatile pollutant (such as coke powder) is removed, then are passed through Flowed out after the fractionating system processing for crossing catalytic cracking unit with catalytic cracking liquefied petroleum gas, mixed liquor Liquefied oil gas compared to coking liquefied petroleum gas and catalytic liquefied petroleum gas direct mixture in sulfur content And relative reduction in non-mercaptan sulfur proportion, and relatively easily remove.
The present invention is by coking liquefied petroleum gas is by the processing of catalytic cracking unit and is merged into catalytic liquefaction Refined in the desulfuration purification device of oil gas, by entering promoting the circulation of qi to the catalytic liquefied petroleum gas after refining Body is fractionated, and concentrate propylene can improve the yield of crude propylene yield and MTBE products (by carrying For more isobutyl olefinic constituents so as to produce more MTBE), and operating process is simplified, drop Low running cost.
In the present invention, carry molten as the back suction in mercaptan extraction device using the liquefied petroleum gas after desulfurization Agent, because it does not contain the aromatic component easily emulsified with alkali lye, produced by removing during alkali liquid regeneration Effect is notable during disulphide, and returns to catalytic cracking prompting pipe reactor processing after use, so The material outside device is not needed to be used as back suction extraction solvent, it is not required that in hydrotreating in addition, operation more It is convenient.
Brief description of the drawings
Fig. 1 exemplarily illustrates the preferred embodiment of the present invention.
Fig. 2 is the schematic flow sheet of extraction desulfurization process for purification in the prior art.
Fig. 1 is only intended to usually represent the flow of a preferred embodiment of the present invention, and be not intended to Go out about container, heater, cooler, pump, compressor reducer, valve, control device of technical process etc. in detail Feelings, these are basic equipment for people familiar with the art.
Refinery coker feedstocks enter coking plant 4 through pipeline 3 and handled, resulting coking liquefied petroleum gas The riser of catalytic cracking unit 2 is passed through by pipeline 5, with entering catalytic cracking unit 2 through pipeline 1 Catalytically cracked material carry out catalytic cracking reaction together, so as to obtain a kind of liquefied petroleum gas of mixing, The mixed liquefied oil gas enters the removing of hydramine extraction device 7 hydrogen sulfide through pipeline 6, and (not shown hydramine takes off Adsorption device) and enter conventional caustic extraction device through pipeline 8, remove mercaptan through caustic extraction unit 9 The liquefied petroleum gas product after being refined is discharged by pipeline 10.And flowed out through caustic extraction unit 9 The alkali lye for absorbing mercaptan flow into alkali liquor oxidized unit 12 through pipeline 11, air (not shown) with In the presence of oxidation catalyst, the mercaptides in alkali lye is oxidized to disulphide, and alkali lye is regenerated. Through discharge air after the regeneration alkali lye for being mixed with disulphide through pipeline 13 and shunted from pipeline 10, And liquefied petroleum gas is mixed into the anti-progress of extraction unit 15 back suction after being refined through the next part of the stream of pipeline 14 Operation is proposed, the disulphide is carried in a part of refining liquefied petrolium gas (LPG) by back suction, is mixed with two A part of refining liquefied petrolium gas (LPG) of sulfide is discharged after being separated with regeneration alkali lye through pipeline 16, and is returned To the circular treatment of catalytic cracking unit 2, and the regeneration alkali lye (not shown) after separating returns to alkali lye and taken out Bill of lading member 9 is recycled.
Fig. 2 is prior art flow.From unlike schematic diagram 1 of the present invention, from coking plant 3 Coking liquefied petroleum gas is through pipeline 5 and the catalytic cracking gasoline gas from catalytic cracking unit 2 in pipeline 6 Mixing, then obtains essence through conventional hydramine extracting removing hydrogen sulfide with conventional caustic extraction removing mercaptan Liquefied petroleum gas product after system.Wherein in anti-extraction unit 15, generally using the material outside this flow (such as naphtha after being hydrogenated with) (is flowed into) as back suction extraction solvent through pipeline 14, and generally completes anti- After extraction procedure device outside this flow (such as Naphtha hydrofining unit) is passed out to through pipeline 16 separately Processing.
Embodiment
Below in conjunction with embodiment, the invention will be further described.Embodiment is intended to usually represent this hair The flow of a bright preferred embodiment, and be not intended to provide relevant container, heater, cooler, The details such as pump, compressor reducer, valve, the control device of technical process, these are to people familiar with the art For be basic equipment.Given embodiment is intended to illustrate invention, and not in any way The limitation present invention.
Embodiment 1
Certain refinery produces coking liquefied petroleum gas from coking plant, and sulfur content is down to about after being handled through hydramine 3000mg/m3, then after caustic extraction sulfur content is down to 200mg/m3~300mg/m3Left and right.
The refinery produces catalytic liquefied petroleum gas from catalytic cracking unit, and sulfur content is down to after being handled through hydramine About 200mg/m3, then after caustic extraction sulfur content is down to 5mg/m3。
According to the present invention, the coking liquefied petroleum gas for originating from coking plant is connected to catalysis by pipeline and split Disguise the riser reactor put, and sprayed into by nozzle, coking liquefied petroleum gas and catalytically cracked material Occurs cracking reaction in riser together.Then mixed liquor is distillated from the fractionating system of catalytic cracking unit Liquefied oil gas, the mixed liquefied oil gas include cracking handle after coking liquefied petroleum gas and with by urging Change the catalytic liquefied petroleum gas that cracked stock cracking is produced.Sulphur after the mixed liquefied oil gas is extracted through hydramine Content about 250mg/m3, then after caustic extraction sulfur content is down to 10mg/m3。
Wherein, in the back suction drop handle section of mercaptan extraction unit, using the liquefied petroleum gas after desulfurization as anti- Extract the solvent of disulphide, back suction extraction solvent and alkali lye volume ratio 3:7, and arrived in sulfur content accumulation μ g/g of 6000 μ g/g~10000 or so are discharged to catalyst cracker processing.
If as can be seen that coking liquefied petroleum gas is handled without catalytic cracking, through hydramine extracting and alkali After liquid extracting, sulfur content can only be down to 200mg/m3~300mg/m3Left and right, if but through catalytic cracking Pretreatment, then again after same hydramine extracting and caustic extraction, sulfur content can be down to 10mg/m3 Hereinafter, the good result of the present invention is shown.
Embodiment 2
The present embodiment is used to illustrate as back suction extraction solvent to be used for using liquefied petroleum gas after alkali density desulfurization Remove the effect of disulphide in alkali lye.
In the present embodiment, using alkali lye of the sodium hydroxide solution as liquefied petroleum gas alkali density unit, Its mass fraction is 20%, and the μ g/g of 200 μ g/g~500 sulfonated phthalocyanine cobalt (commercially available product) has been dissolved in alkali lye, The alkali liquor oxidized regeneration for making to absorb mercaptan as oxidation catalyst.
The refined operating procedure of extraction desulfurization is specific as follows：
By sodium hydroxide lye and the liquefaction after alkanolamine solution (40%MDEA solution) removing hydrogen sulfide Oil gas is contacted in extraction system, and the mercaptan in liquefied petroleum gas is transferred in alkali lye, the liquefaction after desulfurization Oil gas turns into product and sends into tank field, wherein, the volume ratio of alkali lye and liquefied petroleum gas is 2:8, temperature 40 DEG C, pressure 1.4MPa；Absorb mercaptan alkali lye separated with liquefied gas after enter oxidative system processing, Wherein, it is injected into as the air of oxidant according to two times of the theoretical amount of oxidation mercaptides in oxidative system, The pressure of oxidative system is 0.35MPa, and temperature is 55 DEG C, and the mercaptan sodium salt in alkali lye is oxidized to two sulphur Compound is so that alkali liquid regeneration；Alkali lye after oxidation is mixed with unnecessary air, disulphide, in release Enter anti-extraction system after air tail gas to contact with back suction extraction solvent, wherein using the liquefied petroleum gas after desulfurization As back suction extraction solvent, the volume ratio with alkali lye is 3:7, back suction extraction solvent is recycled, and back suction, which is carried, is The pressure of system is 1.4MPa, and temperature is 40 DEG C；Back suction carry after alkali lye return to extraction system circulation make With.
As a comparison, it is another using refinery's treated gasoline product (sulfur content is not more than 50 μ g/g, 33 DEG C of boiling range~ 200 DEG C) as back suction extraction solvent, other technological parameters are just as simply the pressure of anti-extraction system is down to 0.35MPa。
Table 1 gives the determination data of remaining disulphide sulfur content in the regeneration alkali lye after back suction is carried, its Sulfur content is determined as follows：The quality such as rear alkali lye are carried using 90 DEG C of -120 DEG C of petroleum ethers (no sulphur) and back suction It is sufficiently mixed, back suction is carried disulphide remaining in rear alkali lye and be transferred in petroleum ether, then stands and divide From sulfur content in rear survey petroleum ether, this sulfur content value just carries remaining disulphide sulphur in rear alkali lye for back suction and contained Amount.
Table 1
Used it can be seen from the data of table 1 using the liquefied petroleum gas after desulfurization as back suction extraction solvent When, back suction puies forward disulphide sulfur content in rear alkali lye and is much smaller than using treated gasoline as back suction extraction solvent Situation when using, the effect for showing to use the liquefied petroleum gas after desulfurization to be used as back suction extraction solvent will More preferably.It also found in operation, using treated gasoline as back suction extraction solvent in use, back suction carries rear alkali lye In remaining disulphide it is sometimes quite a lot of, this is probably caused by it there occurs the emulsification with alkali lye.
It can be deduced that using the liquefied petroleum gas after desulfurization as back suction extraction solvent when, alkali lye is effectively utilized Rate can be higher, and alkali lye discharge can be less.

Claims (8)

1. a kind of desulfurization refining method of mixed liquefied oil gas, comprises the following steps：
(1) catalytic cracking that the coking liquefied petroleum gas from coking plant is passed through into catalytic cracking unit is lifted Pipe reactor, occurs cracking reaction, coking together with entering the catalytically cracked material in catalytic cracking riser The hydrocarbon component of relative macromolecular in liquefied petroleum gas and sulfide change into respectively the hydro carbons of relative small molecule with Sulfide；
(2) occur the coking liquefied petroleum gas of cracking reaction and the catalytic liquid by catalytically cracked material cracking Liquefied oil gas flows out together from the fractionating system of catalytic cracking unit, enters hydrogen sulfide extraction unit extracting removing sulphur Change hydrogen, then flow into mercaptan extraction unit extracting removing mercaptan, the mixed liquefied gas after desulfurization turns into low-sulfur Liquefied petroleum gas product.
2. the method for claim 1, it is characterised in that the coking liquefied petroleum gas is sprayed into by nozzle In the catalytic cracking riser reactor of catalytic cracking unit.
3. the method for claim 1, it is characterised in that carry out the mixed liquefied oil gas after the desulfurization Washing is handled with coalescence, then as product.
4. the method for claim 1, it is characterised in that the mixed liquefied oil gas sulfur content after the desulfurization No more than 10 μ g/g.
5. the method for claim 1, it is characterised in that the hydrogen sulfide extraction unit is extracted using hydramine Mode, including hydramine extracting and hydramine desorption process.
6. the method for claim 1, it is characterised in that mercaptan extraction unit by the way of caustic extraction, Three processes are put forward including caustic extraction, alkali liquor oxidized and back suction.
7. the method for claim 6, it is characterised in that the mixed liquefied oil gas after desulfurization is separated one It is allocated as the back suction extraction solvent for anti-extractive process.
8. the method for claim 7, it is characterised in that the mixed liquefied oil gas after a part of desulfurization Carried by back suction after the disulphide in removing regeneration alkali lye, again return to catalytic cracking riser reactor Processing.
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