CN104277880A - Method for absorbing and separating light hydrocarbons from dry gas or industrial tail gas by utilizing ionic liquid - Google Patents
Method for absorbing and separating light hydrocarbons from dry gas or industrial tail gas by utilizing ionic liquid Download PDFInfo
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- CN104277880A CN104277880A CN201410447381.8A CN201410447381A CN104277880A CN 104277880 A CN104277880 A CN 104277880A CN 201410447381 A CN201410447381 A CN 201410447381A CN 104277880 A CN104277880 A CN 104277880A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1412—Controlling the absorption process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1418—Recovery of products
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- 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
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/04—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas with liquid absorbents
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- 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
- C10G2300/10—Feedstock materials
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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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Abstract
The invention discloses a method for absorbing and separating light hydrocarbons from dry gas or industrial tail gas by utilizing an ionic liquid. The ionic liquid or a mixed solvent of the ionic liquid and a molecular solvent is taken as an absorbent to be in contact with the dry gas or the industrial tail gas, an absorption liquid containing the light hydrocarbons is obtained by absorption and the light hydrocarbons are further obtained by desorption and separation; and the light hydrocarbons are alkanes or olefins which mainly contain C2-C4. The invention provides the method for absorbing and separating the light hydrocarbons from the dry gas or the industrial tail gas by utilizing the ionic liquid. The ionic liquid or the mixed solvent of the ionic liquid and the molecular solvent is taken as the absorbent, an absorption-desorption method is adopted for recovery and separation of the light hydrocarbons, and the absorbent has very high solubility of the light hydrocarbons and separation selectivity, so that efficient separation and recovery of the light hydrocarbons can be realized and the highest comprehensive recovery rate can achieve 98.5%.
Description
Technical field
The present invention relates to the separation of dry gas and industrial tail gas and reclaim purification art, being specifically related to a kind of method utilizing ionic liquid absorption extraction lighter hydrocarbons from dry gas or industrial tail gas.
Background technology
The refinery dry gas produced by heavy oil fluid catalytic cracking, thermally splitting, delayed coking etc., and the tail gas etc. of chemical industry equipment discharge, lighter hydrocarbons resource containing certain content, but they are admitted to gas pipe network usually as fuel gas, cause the low-grade utilization of resource.Therefore from dry gas and industrial tail gas, reclaim lighter hydrocarbons there is important practical significance and economic implications.
At present, the industrial separation method to hydro carbons gas mixtures such as dry gas mainly separation by deep refrigeration, solvent absorption, absorption and rectifying integrated separation method.First method utilizes the relative volatility of each component in hydro carbons gas mixture different, and condensation at low temperatures, then carries out multicomponent rectification separation in rectifying tower, afterwards under different rectification temperatures, each component is separated one by one; Latter two method utilizes the different solubility of each component in certain absorption agent in gas mixture, realizes the selective absorbing of lighter hydrocarbons with absorption agent, or absorbs the method for rear rectifying, and each component is separated one by one from absorption agent.
Early 1990s, it is first-generation ARS (the Adcanced Recovery System) technology of core and the s-generation ARS technology being core with heat-integrated distillation system (HRS) being separated for hydro carbons that Stone & Webster company of the U.S. successively develops with fractionator, and product purity can reach polymerization-grade.
The deep cooling process for separating of Mobil company of the U.S. and Air Products company joint development is formal suitability for industrialized production in 1987, makes yield of ethene in fluidized catalytic cracking (FFC) technique reach 90% ~ 98%.
Publication number is disclose a kind of employing two rectifying tower in the american documentation literature of US4718986 from C
4the technique of more than 99wt% 1-butylene is prepared in hydrocarbon mixture.In this technique, C
4mixture is in first rectifying tower, and component Trimethylmethane is discharged from tower top, and heavy constituent imports second rectifying tower from tower reactor, obtains the 1-butylene of purity 99wt% from the tower top of second tower, and tower reactor obtains the mixture of normal butane, 2-butylene and 1-butylene.
Publication number is the recovery method disclosing a kind of light hydrocarbon in natural gas in the Chinese patent literature of CN1414067A, after the shallow cold technique of Sweet natural gas, products therefrom is imported in secondary triphase separator and carries out gas-liquid separation, gas enters the natural gas and oil C in the bottom on absorption tower and absorption tower
5+ carry out gas-liquid to exchange generation C
3, C
4component, then reclaims; Liquid enters desorption tower after mixing with the lighter hydrocarbons in secondary triphase separator, removes methane and ethane, and stripping liquid enters next stage desorption tower and obtains C
3, C
4reclaim after component.But the method is only applicable to reclaim C from Sweet natural gas
3, C
4, and be not suitable for the recovery of lighter hydrocarbons in dry gas and industrial tail gas, and the volatile loss of absorption agent.
Publication number is the absorption process that the Chinese patent literature of CN1640992A discloses a kind of refrigeration oil, adopts device self-produced stable light hydrocarbon mixture to make absorption agent, and consumption is less and can obtain higher light hydrocarbon recovery rate, and technique is also simpler.But the method is only applicable to reclaim liquefied gas from associated gas or Sweet natural gas, can not reclaim C
2fraction, the volatile loss of absorption agent also, also cannot be used for the recovery of lighter hydrocarbons in dry gas and industrial tail gas.
Publication number is the method that the Chinese patent literature of CN 101063048A discloses cold oil absorption extraction plant catalytic dry gas in a kind of employing, comprise compression, remove sour gas, dry decontamination, absorption, desorb, the step composition such as cold recovery and rough segmentation, the liquefied gas adopting refinery to produce makes absorption agent, have with low cost, lose the advantages such as low.But need in this technique dry gas to be cooled to-30 ~-40 DEG C, cold separating technology in belonging to, therefore invest comparatively large, energy consumption is higher.
Although existing technique is more ripe, but separation by deep refrigeration energy consumption is huge, generally be applicable to the recovery of extensive alkene, and the absorption agent adopted in absorption process is molecular solvent, there is the deficiencies such as volatile, poor heat stability, be difficult to complete recycling use, and easily cause the pollution of environment and product.Therefore, be necessary development of new lyosorption and absorption process, the selectivity that raising dry gas is separated with lighter hydrocarbons in industrial tail gas and absorptive capacity.
Summary of the invention
The invention provides a kind of method utilizing ionic liquid absorption extraction lighter hydrocarbons from dry gas or industrial tail gas, using the mixed solvent of ionic liquid or ionic liquid and molecular solvent as absorption agent, adopt the method for absorption-desorb, reclaim and be separated lighter hydrocarbons, described absorption agent has very high lighter hydrocarbons solubleness and separation selectivity, and the high efficiency separation that can realize lighter hydrocarbons reclaims.
The gas mixture of multiple gases of dry gas for producing in the oil product course of processing, gas mixture is mainly containing nitrogen, hydrogen, methane, ethane, ethene, propane, propylene, carbon monoxide, carbonic acid gas, C
4above hydro carbons, water vapour and the non-condensable gases such as helium, argon gas; Described industrial tail gas is the waste gas of various processing unit discharge, and gas mixture is mainly containing nitrogen, hydrogen, methane, ethane, ethene, propane, propylene, carbon monoxide, carbonic acid gas, C
4above hydro carbons, water vapour and the non-condensable gases such as helium, argon gas.
The invention discloses a kind of method utilizing ionic liquid absorption extraction lighter hydrocarbons from dry gas or industrial tail gas, comprise the steps:
Using the mixing solutions of ionic liquid or ionic liquid and molecular solvent as absorption agent, contact with dry gas or industrial tail gas, absorb the absorption liquid obtained containing lighter hydrocarbons, then obtain lighter hydrocarbons through Desorption separation;
Described lighter hydrocarbons are main containing C
2~ C
4alkane or alkene.
The residual exhaust obtained after absorption agent absorbs is hydrogen, nitrogen, carbon monoxide, carbonic acid gas, methane, water vapor and the non-condensable gases such as helium, argon gas.
Described ionic liquid is by positively charged ion M
+and anion N
-two portions form, and find after deliberation, anion N
-the upper ionic liquid containing long alkyl chain has very high lighter hydrocarbons solubleness, to C
2~ C
4lighter hydrocarbons there is very high separation selectivity, and there is the features such as low, the wide liquid journey of viscosity, be suitable for the separation of lighter hydrocarbons.
As preferably, described anion N
-for the long-chain fat acid anion (C that carbon number is 6 ~ 22
nh
2n+1cOO
-, n=5 ~ 21), carbon number be 4 ~ 12 chain alkyl sulphonate negatively charged ion (C
nh
2n+1sO
4 -, n=4 ~ 12), carbon number be 4 ~ 12 chain alkyl phosphoric acid ester negatively charged ion ((C
nh
2n+
1)
2pO
4 -, n=4 ~ 12), carbon number be 4 ~ 12 chain alkyl phosphorous acid ester negatively charged ion (C
nh
2n+1hPO
3 -, n=4 ~ 12) in one;
Described positively charged ion M
+for the one in imidazole type positively charged ion, quaternary phosphine type positively charged ion, quaternary ammonium cation, tetramethyleneimine type positively charged ion.Preferably there is substituent imidazole type positively charged ion, there is substituent quaternary phosphine type positively charged ion, there is substituent quaternary ammonium cation, the one had in substituent tetramethyleneimine type positively charged ion.On described imidazole type positively charged ion, quaternary phosphine type positively charged ion, quaternary ammonium cation and tetramethyleneimine type positively charged ion with substituting group independent separately, and its kind strictly not to be limited, can C be selected
4~ C
16alkyl, substituent number can be monosubstituted or polysubstituted (as two replace or three replace etc.), substituting group time polysubstituted in different loci can be the same or different.
For the ionic liquid with viscosity higher, then can add molecular solvent wherein as thinner, improve mobility, form the mixed solvent of ionic liquid and molecular solvent, carry out absorption extraction.
As preferably, described molecular solvent is C
6~ C
16hydro carbons, aromatic hydrocarbons, DMF, dimethyl sulfoxide (DMSO), tetramethylene sulfone or water; Described aromatic hydrocarbons can be benzene,toluene,xylene etc.
As preferably, the percent by volume of the mixed solvent Middle molecule solvent of described ionic liquid and molecular solvent is 0.1 ~ 20%.
But in order to more completely reclaim absorption agent, reaching and better deviating from effect, preferred pure ionic liquid makes absorption agent as much as possible.
Further preferably, described ionic liquid is 4-butyl-phosphonium n-caprylic acid salt, TBuA n-caproic acid salt, three hexyl Shi tetra-Wan Ji Phosphonium lauroleates, N, N-butyl ethyl tetramethyleneimine sulfate pentahydrate, N, N-butyl methyl tetramethyleneimine phosphorous acid butyl ester, the own ester of 1-butyl-2,3-methylimidazole phosphorous acid or three hexyl tetradecyl ammonium dibutyl phosphates.Above-mentioned preferred ionic liquid is all to C
2~ C
4lighter hydrocarbons there is splendid solubleness and the separation selectivity of excellence, the rate of recovery of lighter hydrocarbons is all higher than 91%.
Again further preferably, described ionic liquid is 4-butyl-phosphonium n-caprylic acid salt, and it is to C
2~ C
4the rate of recovery of lighter hydrocarbons is up to 98.5%.
As preferably, absorption agent contacts absorption of light hydrocarbon condition with dry gas or industrial tail gas is: temperature is 5 ~ 20 DEG C, and pressure is 1.0 ~ 5.0MPa; Further preferably: absorption temperature is 10 DEG C, absorption pressure is 2.0MPa.Research shows that temperature is too low, and the mobility of ionic liquid is deteriorated, and temperature is too high, and the solubleness of lighter hydrocarbons significantly declines, and higher absorption pressure is conducive to de-lighter hydrocarbons.
Desorption separation can adopt intensification desorb, also can heat up, reduces pressure and use desorb; As preferably, described Desorption separation condition is: temperature is 35 ~ 80 DEG C, and pressure is 0.1 ~ 0.8MPa; More preferably: desorption temperature is 75 DEG C, desorption pressures is 0.2MPa.
The described concrete steps of ionic liquid method of absorption extraction lighter hydrocarbons from dry gas or industrial tail gas that utilize are: absorption agent is cooled to 5 ~ 20 DEG C, under pressure is 1.0 ~ 5.0MPa, contact with the dry gas or industrial tail gas that are cooled to 5 ~ 20 DEG C, absorb the absorption liquid obtained containing lighter hydrocarbons, lighter hydrocarbons are obtained again through Desorption separation, desorption temperature is 35 ~ 80 DEG C, and desorption pressures is 0.1 ~ 0.8MPa.
As preferably, the way of contact of described absorption agent and dry gas or industrial tail gas is counter current contact, can improve mass transfer effect better.
Compared with prior art, tool of the present invention has the following advantages:
1. adopt ionic liquid as absorption agent, the thermostability had, extremely low saturated vapor pressure, the repeatedly recycling of absorption agent can be realized by heating under reduced pressure, and ionic liquid steam can not be produced and product is polluted in desorption of gases.
2. the ionic liquid containing long alkyl chain on the anion structure designed by the present invention not only has very high lighter hydrocarbons solubleness, and there is very high lighter hydrocarbons separation selectivity, and this kind of viscosity of il is lower, be conducive to the mass transfer diffusion of absorption process, significantly be better than traditional volatile organic solvent as absorption agent, thus achieve the efficient removal of lighter hydrocarbons.
3. the inventive method with ionic liquid or the mixed solvent that is made up of ionic liquid and molecular solvent for absorption agent, adopt the method for absorption-desorb, reclaim the lighter hydrocarbons in dry gas or industrial tail gas, and the continuous circulation that can realize ionic liquid uses, and has that separation efficiency is high, solvent consumption is few, safety and environmental protection, be suitable for the advantages such as suitability for industrialized production.
Embodiment:
Utilize the concrete steps of ionic liquid method of absorption extraction lighter hydrocarbons from dry gas or industrial tail gas as follows in the present invention:
1, dry gas or industrial tail gas are forced into 1.0MPa ~ 5.0MPa through compressor, temperature is made to be down to 5 ~ 20 DEG C by cooling, pass into from the bottom on absorption tower, the absorption agent being cooled to 5 ~ 20 DEG C is added from the tower top on absorption tower, obtain the absorption liquid being rich in lighter hydrocarbons at the bottom of tower, tower top obtains the residual exhaust into hydrogen, nitrogen, carbon monoxide, carbonic acid gas, methane, water vapor and the non-condensable gases such as helium, argon gas.
2, the absorption liquid being rich in lighter hydrocarbons enters desorption tower from below, and adopt the method for intensification desorb, desorption temperature controls at 35 ~ 80 DEG C, or employing heats up, reduces pressure and use desorb, and pressure range is 0.1 ~ 0.8MPa, and tower top obtains C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent, and can be used for recycle and reuse.
Embodiment 1
Absorption agent forms: [P
4444] [C
7h
15cOO] the pure ionic liquid absorption agent of 4-butyl-phosphonium n-caprylic acid salt.Oil refinery dry gas composition (mol ratio): methane 23.0%, ethane 20.1%, ethene 16.8%, propane 2.3%, propylene 5.2%, hydrogen 1.1%, nitrogen 22.4% and C
4other components above.
Oil refinery dry gas is forced into 2.0MPa through compressor, and make temperature be down to 10 DEG C by cooling, pass into bottom absorbing tower, absorption tower tower top adds absorption agent, guarantees wherein most C
2~ C
4lighter hydrocarbons are absorbed, and what obtain at the bottom of tower is rich in C
2~ C
4the absorption liquid of lighter hydrocarbons, tower top obtains the residual exhaust such as nitrogen, hydrogen, methane of insoluble.
At the bottom of tower, absorption liquid enters desorption tower, and adopt the method for intensification desorb, desorption temperature controls at 75 DEG C, and pressure is 0.2MPa, and tower top obtains C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent, recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 98.5%.
Embodiment 2
Absorption agent forms: [N
4444] [C
5h
11cOO] the pure ionic liquid absorption agent of TBuA n-caproic acid salt.Oil refinery dry gas forms: methane 24%, ethane 9.0%, ethene 7.1%, propane 0.3%, propylene 1.2%, hydrogen 32%, air 19% and C
4other components above.
As embodiment 1, dry gas and absorption agent are at 15 DEG C, and under 2.0MPa, counter current contact absorbs, and absorption liquid separates sucking-off C at 70 DEG C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 92.1%.
Embodiment 3
Absorption agent forms: [bmpyrr] [BuHPO
3] N, N-butyl methyl tetramethyleneimine phosphorous acid butyl ester ionic liquid and C
6the composite absorber of hydro carbons, ionic liquid accounts for 80% (volume fraction).Dry gas forms: methane 19%, ethane 12.3%, ethene 14.5%, propane 0.5%, propylene 1.3%, hydrogen 28%, air 18% and C
4other components above.
As embodiment 1, dry gas and absorption agent 10 DEG C, counter current contact absorbs under 3.5MPa, absorption liquid 75 DEG C, the decompression that heats up under 0.2MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 96.3%.
Embodiment 4
Absorption agent forms: [P
666 (14)] [C
11h
23cOO] composite absorber of three hexyl Shi tetra-Wan Ji Phosphonium lauroleate ionic liquids and water, ionic liquid volume fraction is 96%.Dry gas forms: methane 31%, ethane 7.2%, ethene 6.8%, propane 0.2%, propylene 1.2%, hydrogen 32%, air 19% and C
4other components above.
As embodiment 1, tail gas and absorption agent 8 DEG C, counter current contact absorbs under 4.2MPa, absorption liquid 68 DEG C, the decompression that heats up under 0.6MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 93.4%.
Embodiment 5
Absorption agent forms: [bmmim] [HexHPO
3] the own ester ionic liquid of 1-butyl-2,3-methylimidazole phosphorous acid.Industrial tail gas consists of (mol ratio): ethane 3.0%, ethene 22.3%, propane 5.5%, propylene 0.3%, hydrogen 1.9%, nitrogen 50.3% and C
4other components above.
As embodiment 1, tail gas and absorption agent 15 DEG C, counter current contact absorbs under 2.8MPa, absorption liquid heats up at 80 DEG C and separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 95.7%.
Embodiment 6
Absorption agent forms: [bepyrr] [BuSO
4] N, N-butyl ethyl tetramethyleneimine sulfate pentahydrate ionic liquid and DMF composite absorber, ionic liquid volume fraction is 85%.Dry gas forms: methane 14%, ethane 15.2%, ethene 18.6%, propane 0.8%, propylene 1.5%, hydrogen 25%, air 21% and C
4other components above.
As embodiment 1, dry gas and absorption agent 10 DEG C, counter current contact absorbs under 2.3MPa, absorption liquid 65 DEG C, the decompression that heats up under 0.1MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 95.5%.
Embodiment 7
Absorption agent forms: [N
666 (14)] [Bu
2pO
4] composite absorber of three hexyl tetradecyl ammonium dibutyl phosphate ionic liquids and tetramethylene sulfone, ionic liquid volume fraction is 92%.Industrial tail gas consists of (mol ratio): ethane 2.2%, ethene 24.1%, propane 5.2%, propylene 0.3%, hydrogen 1.4%, nitrogen 50.5% and C
4other components above.
As embodiment 1, dry gas and absorption agent 20 DEG C, counter current contact absorbs under 4.5MPa, absorption liquid 75 DEG C, the decompression that heats up under 0.2MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons can reach 91.9%.
Comparative example 1
Absorption agent forms: [bmim] [OAc] 1-butyl-3-Methylimidazole acetate ionic liquid.Dry gas forms: methane 15.3%, ethane 13.4%, ethene 15.8%, propane 0.8%, propylene 1.4%, hydrogen 32%, air 19% and C
4other components 2.3% above.
As embodiment 1, dry gas and absorption agent 10 DEG C, counter current contact absorbs under 2.0MPa, absorption liquid 75 DEG C, the decompression that heats up under 0.2MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons is 83.9%.
Comparative example 2
Absorption agent forms: [bmpyrr] [Me
2pO
4] N, N-butyl methyl tetramethyleneimine dimethyl phosphate ionic liquid.Dry gas forms: methane 13.3%, ethane 13.9%, ethene 16.6%, propane 0.9%, propylene 1.5%, hydrogen 32%, air 18% and C
4other components 3.8% above.
As embodiment 1, dry gas and absorption agent 20 DEG C, counter current contact absorbs under 2.3MPa, absorption liquid 70 DEG C, the decompression that heats up under 0.3MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons is 86.3%.
Comparative example 3
Absorption agent forms: [bmmim] [MeSO
4] 1-butyl-2,3-methylimidazole methyl sulfate ion liquid.Dry gas forms: methane 9.8%, ethane 14.9%, ethene 22.7%, propane 1.1%, propylene 1.7%, hydrogen 29%, air 17% and C
4other components 3.8% above.
As embodiment 1, dry gas and absorption agent 20 DEG C, counter current contact absorbs under 2.3MPa, absorption liquid 80 DEG C, the decompression that heats up under 0.2MPa separates sucking-off C
2~ C
4lighter hydrocarbons, be absorbed at the bottom of tower agent recycle and reuse.C
2~ C
4the comprehensive recovery of lighter hydrocarbons is 80.2%.
Claims (8)
1. utilize a method for ionic liquid absorption extraction lighter hydrocarbons from dry gas or industrial tail gas, it is characterized in that, comprise the steps:
Using the mixed solvent of ionic liquid or ionic liquid and molecular solvent as absorption agent, contact with dry gas or industrial tail gas, absorb the absorption liquid obtained containing lighter hydrocarbons, then obtain lighter hydrocarbons through Desorption separation;
Described lighter hydrocarbons are main containing C
2~ C
4alkane or alkene.
2. method according to claim 1, is characterized in that, described ionic liquid is by positively charged ion M
+and anion N
-two portions form, anion N
-for the one that carbon number be 6 ~ 22 long-chain fat acid anion, the carbon number chain alkyl sulphonate negatively charged ion that is 4 ~ 12, the carbon number chain alkyl phosphoric acid ester negatively charged ion that is 4 ~ 12, carbon number are in the chain alkyl phosphorous acid ester negatively charged ion of 4 ~ 12; Positively charged ion M
+for the one in imidazole type positively charged ion, quaternary phosphine type positively charged ion, quaternary ammonium cation, tetramethyleneimine type positively charged ion.
3. method according to claim 1, is characterized in that, described molecular solvent is C
6~ C
16hydro carbons, aromatic hydrocarbons, DMF, dimethyl sulfoxide (DMSO), tetramethylene sulfone or water;
The percent by volume of the mixed solvent Middle molecule solvent of described ionic liquid and molecular solvent is 0.1 ~ 20%.
4. the method according to the arbitrary claim of claims 1 to 3, is characterized in that, described absorption agent is ionic liquid.
5. method according to claim 4, it is characterized in that, described ionic liquid is 4-butyl-phosphonium n-caprylic acid salt, TBuA n-caproic acid salt, three hexyl Shi tetra-Wan Ji Phosphonium lauroleates, N, N-butyl ethyl tetramethyleneimine sulfate pentahydrate, N, N-butyl methyl tetramethyleneimine phosphorous acid butyl ester, the own ester of 1-butyl-2,3-methylimidazole phosphorous acid or three hexyl tetradecyl ammonium dibutyl phosphates.
6. the method according to claim 1 or 2 or 5, is characterized in that, absorption agent contacts absorption of light hydrocarbon condition with dry gas or industrial tail gas is: temperature is 5 ~ 20 DEG C, and pressure is 1.0 ~ 5.0MPa;
Described Desorption separation condition is: temperature is 35 ~ 80 DEG C, and pressure is 0.1 ~ 0.8MPa.
7. method according to claim 6, it is characterized in that, absorption agent is cooled to 5 ~ 20 DEG C, under pressure is 1.0 ~ 5.0MPa, contact with the dry gas or industrial tail gas that are cooled to 5 ~ 20 DEG C, absorb the absorption liquid obtained containing lighter hydrocarbons, then obtain lighter hydrocarbons through Desorption separation, desorption temperature is 35 ~ 80 DEG C, and desorption pressures is 0.1 ~ 0.8MPa.
8. method according to claim 7, is characterized in that, the way of contact of described absorption agent and dry gas or industrial tail gas is counter current contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447381.8A CN104277880B (en) | 2014-05-14 | 2014-09-04 | A method of using ionic liquid from dry gas or industrial tail gas absorption and separation lighter hydrocarbons |
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Cited By (8)
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| CN105802686A (en) * | 2016-03-08 | 2016-07-27 | 安庆凯美特气体有限公司 | Method for extracting liquefied gas and pentane from refinery tail gas |
| CN106731489A (en) * | 2015-11-24 | 2017-05-31 | 中国科学院大连化学物理研究所 | A kind of method of use fluoride ion liquid high-temperature digestion hydrocarbon gas |
| CN107398146A (en) * | 2017-08-16 | 2017-11-28 | 天津大学 | A kind of protonized ionic liquid absorbent containing metal salt and its application |
| CN107774095A (en) * | 2016-08-25 | 2018-03-09 | 四川天采科技有限责任公司 | A kind of natural gas is dehydrated the full temperature journey pressure swing adsorption purge method of de- hydrocarbon simultaneously |
| CN108640193A (en) * | 2018-05-22 | 2018-10-12 | 河北工业大学 | A kind of ionic liquid-molecular solvent composite extractant and its application |
| CN108654322A (en) * | 2018-05-22 | 2018-10-16 | 石河子大学 | A kind of preparation method and application based on alkaline functional ionic liquid blend film |
| CN114075465A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Ionic liquid light hydrocarbon recovery device and method |
| CN114558549A (en) * | 2020-11-27 | 2022-05-31 | 北京驭碳科技有限公司 | Use of carboxylate compounds as absorbents for capturing carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106731489A (en) * | 2015-11-24 | 2017-05-31 | 中国科学院大连化学物理研究所 | A kind of method of use fluoride ion liquid high-temperature digestion hydrocarbon gas |
| CN105802686A (en) * | 2016-03-08 | 2016-07-27 | 安庆凯美特气体有限公司 | Method for extracting liquefied gas and pentane from refinery tail gas |
| CN107774095A (en) * | 2016-08-25 | 2018-03-09 | 四川天采科技有限责任公司 | A kind of natural gas is dehydrated the full temperature journey pressure swing adsorption purge method of de- hydrocarbon simultaneously |
| CN107774095B (en) * | 2016-08-25 | 2020-06-02 | 四川天采科技有限责任公司 | Full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas |
| CN107398146A (en) * | 2017-08-16 | 2017-11-28 | 天津大学 | A kind of protonized ionic liquid absorbent containing metal salt and its application |
| CN108640193A (en) * | 2018-05-22 | 2018-10-12 | 河北工业大学 | A kind of ionic liquid-molecular solvent composite extractant and its application |
| CN108654322A (en) * | 2018-05-22 | 2018-10-16 | 石河子大学 | A kind of preparation method and application based on alkaline functional ionic liquid blend film |
| CN108654322B (en) * | 2018-05-22 | 2020-02-04 | 石河子大学 | Preparation method and application of alkaline functional ionic liquid-based blend membrane |
| CN108640193B (en) * | 2018-05-22 | 2022-01-11 | 河北工业大学 | Application of ionic liquid-molecular solvent composite extracting agent |
| CN114075465A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Ionic liquid light hydrocarbon recovery device and method |
| CN114558549A (en) * | 2020-11-27 | 2022-05-31 | 北京驭碳科技有限公司 | Use of carboxylate compounds as absorbents for capturing carbon dioxide |
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