US20100069696A1 - Process for separating propylene mixed with propane by adsorption in a simulated moving bed - Google Patents
Process for separating propylene mixed with propane by adsorption in a simulated moving bed Download PDFInfo
- Publication number
- US20100069696A1 US20100069696A1 US12/374,911 US37491107A US2010069696A1 US 20100069696 A1 US20100069696 A1 US 20100069696A1 US 37491107 A US37491107 A US 37491107A US 2010069696 A1 US2010069696 A1 US 2010069696A1
- Authority
- US
- United States
- Prior art keywords
- propylene
- desorbent
- stage
- propane
- separating
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
-
- 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
- C10G2400/20—C2-C4 olefins
Definitions
- the invention relates to a process for the production of propylene from a feedstock that contains essentially propane and propylene.
- This feedstock can also contain, in a minority portion, other hydrocarbons that are heavier or lighter than the C3 hydrocarbons.
- These hydrocarbons other than C3 can represent up to 10% by weight of the feedstock to be treated, and preferably represent less than 5% by weight of the feedstock that is to be treated.
- Propylene with a high level of purity is defined as a purity level that is greater than 95.0% by weight, and preferably greater then 97% by weight.
- Propylene is an important intermediate compound in the field of petrochemistry, and it intervenes in particular in the production of polypropylene, acrylonitrile, isopropanol, cumene and oxo alcohols.
- Propylene is primarily produced by steam-cracking or by catalytic cracking of heavy fractions, and it is generally obtained mixed with propane.
- Heavy fraction is defined as a hydrocarbon fraction that typically has a distillation interval of between 200° C. and 450° C., such as, for example, a vacuum distillate or an atmospheric residue.
- any petroleum fraction regardless of its origin, containing for the most part propane and other C3 hydrocarbons, is able to constitute a feedstock for the process according to the invention.
- TSA processes (abbreviation of “Temperature Swing Adsorption” that can be translated by “adsorption process by temperature variation”) use a high-temperature regeneration of the adsorbent solid and generally have low productivities and yields.
- This type of vacuum regeneration brings about a high power consumption.
- n-butane and the n-pentane have been tested as desorbent.
- the use of a 5A zeolite poses aging problems due to the formation of coke that is deposited inside the pores of the 5A zeolite. To limit this phenomenon, an addition of ammonia is necessary. This therefore introduces an additional radical that has to be eliminated from the propylene that is produced.
- this invention also comprises a 13X zeolite, less active than the 5A zeolite that does not exhibit deactivation problems and therefore does not require an addition of ammonia.
- the 5A zeolite contains acid sites that are responsible for the formation of coke when it is sought to adsorb olefins. It is possible to consult, for example, Misk, Joly, Magnoux et al. (2000, Microporous and Mesoporous Materials, Vol. 40, p. 197, a journal whose French title is “Materiau micro et mesoporeux),” Magnoux, Misk, Joly, et al. (1996, Zeolites, Vol. 16, p. 265).
- the patent FR 2,704,158 describes a process for fractionating a mixture in a gaseous-phase simulated moving bed. In a general manner, this patent describes a category of processes for separation by adsorption, without any specific teaching on the separation of a propane/propylene mixture.
- the selection of the desorbent is generally done according to three criteria:
- the object of this invention is to present a process for separating propylene mixed with propane, implemented in a simulated moving bed in the gaseous phase or in the liquid phase, using a 13X faujasite-type zeolite as an adsorbent and a hydrocarbon that comprises 4 or 5 carbon atoms (C4 or C5 hydrocarbons) as desorbent.
- This process does not exhibit aging of the adsorbent and makes it possible to reach a high yield and a high productivity of propylene with low energy consumption.
- FIG. 1 has adsorption isotherms of propylene, propane, isobutane and butene-1 at 373K on a 13X zeolite.
- the curve with squares corresponds to propylene
- the one with triangles corresponds to isobutane
- the one with diamonds corresponds to propane
- the one with dots corresponds to butene-1.
- the partial molar flow rate (on the ordinate) is expressed in millimols per second, and the time (on the abscissa) is expressed in seconds.
- the curve with squares corresponds to propylene
- the one with triangles corresponds to isobutane
- the one with diamonds corresponds to propane
- the partial molar flow rate (on the ordinate) is expressed in millimols per second and the time (on the abscissa) is expressed in seconds.
- the curve with squares corresponds to propylene, the one with triangles corresponds to isobutane, and the one with diamonds corresponds to butene-1.
- FIG. 3 provides a view of the punch-through curve on a bed that is saturated with a propylene/propane mixture (75 mol %/25 mol %) at 373K and 0.15 MPA on a 13X faujasite-type zeolite with isobutane as a desorbent.
- the partial molar flow rate (on the ordinate) is expressed in millimols per second, and the time (on the abscissa) is expressed in seconds.
- the curve with squares corresponds to propylene
- the one with triangles corresponds to isobutane
- the one with diamonds corresponds to propane
- FIG. 3 a provides a view of the punch-through curve on a bed that is saturated with a propylene/propane mixture (75 mol %/25 mol %) at 373K and 0.15 MPa on a 13X faujasite-type zeolite with the butene-1 as desorbent.
- the molar partial flow rate (on the ordinate) is expressed in millimols per second, and the time (on the abscissa) is expressed in seconds.
- the curve with squares corresponds to polypropylene, the one with triangles corresponds to butene-1, and the one with diamonds corresponds to propane.
- FIG. 4 provides a view with a loss of capacity over time of a 5A zeolite and a 13X zeolite, at 458K and 1.83 MPa over a propylene feedstock.
- the ratio between the capacity of the sieve at a given moment and the initial capacity of the sieve (on the ordinate) is expressed in percentages, and the time (on the abscissa) is expressed in hours.
- the curve with diamonds corresponds to the 5A zeolite without ammonia
- the one with squares corresponds to the 5A zeolite with 0.25% by weight of ammonia
- the one with triangles corresponds to the 13X zeolite.
- the invention relates to a process for the production of high-purity propylene by adsorption from a feedstock that contains mostly a mixture of propane and propylene, whereby this feedstock is typically obtained by steam-cracking or fluidized bed catalytic cracking (denoted FCC in abbreviated form), optionally after selective hydrogenation that makes it possible to reduce its diolefin content.
- a typical example of feedstock that can be used in this separation process is a C3 fraction that is obtained from fractionation of an FCC unit.
- the process according to the invention makes use of the technique of the simulated moving bed that is well described in particular in the patent FR 2 704 158.
- the simulated moving bed unit according to the invention will comprise between 4 and 24 beds and preferably between 6 and 20 beds of adsorbent solid.
- one industrial unit can comprise several units or columns that operate in series and/or in parallel.
- the process according to the invention can operate in the gaseous phase or in the liquid phase and comprises the following stages:
- the process can optionally include one of the two following stages or the following two stages:
- High-purity propylene is defined as a propylene content in the effluent of this separation process that is greater than or equal to 90% by weight, and preferably greater than 95% by weight.
- This invention is based on the selection of an adsorbent/desorbent pair that has proven particularly high-performing both in yield and in service life relative to the pairs already disclosed.
- the selected adsorbent is a 13X faujasite zeolite that has a good propane/propylene selectivity and does not have an aging problem.
- the selected desorbent is either butene-1, or isobutane, or a mixture in any proportion of these two components.
- the process according to this invention can operate both in the gaseous phase as well as in the liquid phase with a suitable selection of operating conditions and the shaping of the adsorbent solid.
- the examples present the results of measurements of adsorption isotherms and of piercing/punch-through tests of a propane/propylene mixture with the isobutane as desorbent.
- the adsorption isotherms of propylene, propane and isobutane on a 13X faujasite-type zeolite are measured gravimetrically at 373K.
- the measured isotherms are provided in FIG. 1 .
- FIG. 1 shows the adsorption isotherms of propylene, propane, isobutane and butene-1 at 373K on a 13X zeolite.
- the curve with squares corresponds to propylene
- the one with triangles corresponds to isobutane
- the one with diamonds corresponds to propane
- the one with dots corresponds to butene-1.
- isobutane and butene-1 have suitable adsorption isotherms to be used as desorbent in a simulated moving bed process for separating the propylene from propane.
- isobutane and propylene have an isotherm that is close to the one of propylene ensures that the quantity of desorbent that is necessary to desorb the propylene is not too high.
- isobutane and butene-1 are slightly less adsorbed than the propylene ensures that the propylene that is injected at the feedstock displaces the isobutane or the butene-1, and therefore that the propylene is properly adsorbed.
- the separation of the propylene (piercing and punch-through curve) from a propylene/propane mixture is evaluated at 373K, on a 13X faujasite-type zeolite.
- the adsorbent bed has a length of 0.84 m, with an inside diameter of 2.15 cm.
- the void fraction of the bed or interstitial porosity is 0.395.
- the activation of the adsorbent is carried out in-situ by injecting a flow of nitrogen of 60 liters/hour in standard conditions (273K and 0.1 MPa). The temperature is then increased linearly along a slope of 1K/minute until reaching 593K.
- the temperature is then kept at 593K for 12 hours.
- the operating mode for obtaining the piercing and punch-through curves is as follows:
- the temperature of the column is maintained at 373K and the pressure at 0.15 MPa.
- the effluent from the column is sampled (15 samples during the piercing and 12 samples during the punch-through), then analyzed by gas chromatography so as to determine its composition at different time intervals.
- composition of the feedstock is:
- the piercing and punch-through curves are provided by FIGS. 2 and 3 .
- the curve with squares corresponds to propylene
- the one with triangles corresponds to isobutane
- the one with diamonds corresponds to propane.
- the piercing and punch-through curves are provided by FIGS. 2 a and 3 a .
- the curve with squares corresponds to propylene
- the one with triangles corresponds to butene-1
- the one with diamonds corresponds to propane.
- the partial molar flow rate (on the ordinate) is expressed in millimols per second, and the time (on the abscissa) is expressed in seconds.
- FIG. 3 a provides a view of the punch-through curve on a bed that is saturated with a propylene/propane mixture (75 mol %/25 mol %) at 373K and 0.15 MPa, on a 13X faujasite-type zeolite with butene-1 as desorbent.
- the partial molar flow rate (on the ordinate) is expressed in millimols per second, and the time (on the abscissa) is expressed in seconds.
- the curve with squares corresponds to propylene
- the one with triangles corresponds to butene-1
- the one with diamonds corresponds to propane
- the aging of the 13X faujasite zeolite is studied and compared to that of the 5A zeolite.
- the bed is kept at 458K and 1.83 MPa.
- a propylene flow rate of 0.5 liter/minute is imposed under standard conditions, and the evolution of the adsorption capacity of the sieve is gravimetrically measured regularly.
- FIG. 4 provides a view of the loss in capacity over time of a 5A zeolite and a 13X zeolite, at 458K and 1.83 MPa on a propylene feedstock.
- the ratio between the capacity of the sieve at a given moment and the initial capacity of the sieve (on the ordinate) is expressed by percentages, and the time (on the abscissa) is expressed in hours.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0606827A FR2903981B1 (fr) | 2006-07-24 | 2006-07-24 | Procede de separation du propylene en melange avec du propane par adsorption en lit mobile simule |
FR0606827 | 2006-07-24 | ||
PCT/FR2007/001170 WO2008012410A1 (fr) | 2006-07-24 | 2007-07-06 | Procédé de séparation du propylene en melange avec du propane par adsorption en lit mobile simule |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2007/001170 A-371-Of-International WO2008012410A1 (fr) | 2006-07-24 | 2007-07-06 | Procédé de séparation du propylene en melange avec du propane par adsorption en lit mobile simule |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/722,715 Continuation US10000430B2 (en) | 2006-07-24 | 2015-05-27 | Process for separating propylene mixed with propane by adsorption in a simulated moving bed |
Publications (1)
Publication Number | Publication Date |
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US20100069696A1 true US20100069696A1 (en) | 2010-03-18 |
Family
ID=38008274
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/374,911 Abandoned US20100069696A1 (en) | 2006-07-24 | 2007-07-06 | Process for separating propylene mixed with propane by adsorption in a simulated moving bed |
US14/722,715 Expired - Fee Related US10000430B2 (en) | 2006-07-24 | 2015-05-27 | Process for separating propylene mixed with propane by adsorption in a simulated moving bed |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US14/722,715 Expired - Fee Related US10000430B2 (en) | 2006-07-24 | 2015-05-27 | Process for separating propylene mixed with propane by adsorption in a simulated moving bed |
Country Status (3)
Country | Link |
---|---|
US (2) | US20100069696A1 (fr) |
FR (1) | FR2903981B1 (fr) |
WO (1) | WO2008012410A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220102248A (ko) * | 2021-01-13 | 2022-07-20 | 인하대학교 산학협력단 | 에틸렌 및 에탄 분리용 흡착제 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102011393B1 (ko) | 2016-10-17 | 2019-08-16 | 한국화학연구원 | 탄소수 2개 내지 4개 범위의 올레핀-파라핀 혼합물 분리를 위한 흡착제 및 이를 이용한 올레핀-파라핀 기체 혼합물의 분리 방법 |
CN114456028B (zh) * | 2020-11-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | 一种丙烯/丙烷的分离方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2906795A (en) * | 1957-07-31 | 1959-09-29 | Texaco Inc | Recovery and utilization of normally gaseous olefins |
US3231492A (en) * | 1962-05-16 | 1966-01-25 | Universal Oil Prod Co | Fluid-solid contacting process |
US5744687A (en) * | 1993-11-29 | 1998-04-28 | The Boc Group, Inc. | Process for recovering alkenes from cracked hydrocarbon streams |
US6293999B1 (en) * | 1999-11-30 | 2001-09-25 | Uop Llc | Process for separating propylene from propane |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2675712B1 (fr) * | 1991-04-29 | 1994-08-26 | Ceca Sa | Perfectionnement aux procedes d'epuration des gaz par adsorption sur adsorbants zeolitiques. |
FR2704158B3 (fr) * | 1993-04-21 | 1995-06-16 | Inst Francais Du Petrole | Procédé et dispositif de fractionnement d'un mélange en lit mobile simulé en présence d'un gaz comprimé. |
-
2006
- 2006-07-24 FR FR0606827A patent/FR2903981B1/fr not_active Expired - Fee Related
-
2007
- 2007-07-06 WO PCT/FR2007/001170 patent/WO2008012410A1/fr active Application Filing
- 2007-07-06 US US12/374,911 patent/US20100069696A1/en not_active Abandoned
-
2015
- 2015-05-27 US US14/722,715 patent/US10000430B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2906795A (en) * | 1957-07-31 | 1959-09-29 | Texaco Inc | Recovery and utilization of normally gaseous olefins |
US3231492A (en) * | 1962-05-16 | 1966-01-25 | Universal Oil Prod Co | Fluid-solid contacting process |
US5744687A (en) * | 1993-11-29 | 1998-04-28 | The Boc Group, Inc. | Process for recovering alkenes from cracked hydrocarbon streams |
US6293999B1 (en) * | 1999-11-30 | 2001-09-25 | Uop Llc | Process for separating propylene from propane |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220102248A (ko) * | 2021-01-13 | 2022-07-20 | 인하대학교 산학협력단 | 에틸렌 및 에탄 분리용 흡착제 |
KR102441701B1 (ko) | 2021-01-13 | 2022-09-07 | 인하대학교 산학협력단 | 에틸렌 및 에탄 분리용 흡착제 |
Also Published As
Publication number | Publication date |
---|---|
FR2903981A1 (fr) | 2008-01-25 |
US20150266797A1 (en) | 2015-09-24 |
WO2008012410A1 (fr) | 2008-01-31 |
FR2903981B1 (fr) | 2010-11-05 |
US10000430B2 (en) | 2018-06-19 |
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