WO2001072400A1 - Process for separating hydrocarbons from gases, in particular gases originating from petroleum storage and distribution - Google Patents

Process for separating hydrocarbons from gases, in particular gases originating from petroleum storage and distribution Download PDF

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Publication number
WO2001072400A1
WO2001072400A1 PCT/PL2000/000104 PL0000104W WO0172400A1 WO 2001072400 A1 WO2001072400 A1 WO 2001072400A1 PL 0000104 W PL0000104 W PL 0000104W WO 0172400 A1 WO0172400 A1 WO 0172400A1
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WO
WIPO (PCT)
Prior art keywords
gases
hydrocarbons
column
absorbent
absorption
Prior art date
Application number
PCT/PL2000/000104
Other languages
French (fr)
Inventor
Eugeniusz Krop
Jerzy Badura
Adam JĘDRZEJCZYK
Henryk Kryszczyszyn
Anna Stachowska
Original Assignee
'ejk' Sp. Z O.O.
'naftobazy' Sp. Z O.O.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 'ejk' Sp. Z O.O., 'naftobazy' Sp. Z O.O. filed Critical 'ejk' Sp. Z O.O.
Priority to AU20319/01A priority Critical patent/AU2031901A/en
Publication of WO2001072400A1 publication Critical patent/WO2001072400A1/en

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Classifications

    • 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
    • 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
    • B01D2253/102—Carbon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40001—Methods relating to additional, e.g. intermediate, treatment of process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds

Definitions

  • the present invention relates to the process of purification of gases from hydrocarbons, particularly gases such as a flue gas originating from the hermetization of petroleum products storage and distribution processes, which gases (vapours) comprise a mixture of hydrocarbons, especially C3 to Cg hydrocarbons, with air or another inert gas.
  • gases such as a flue gas originating from the hermetization of petroleum products storage and distribution processes, which gases (vapours) comprise a mixture of hydrocarbons, especially C3 to Cg hydrocarbons, with air or another inert gas.
  • a plant for the implementation of the process comprises an adsorption-desorption section, or carbon adsorbers with a vacuum system, and a hydrocarbon recovery section.
  • a basic disadvantage of the above solution is the necessity to direct all hydrocarbons contained in the flue gas stream to the carbon adsorbers and consequently to use a correspondingly large adsorbent bed.
  • a process for stabilisation of hydrocarbon content and a flow rate of gases directed to a purification plant for purifying them from hydrocarbons comprising subjecting the gases to an adsorption-desorption process on a column in a presence of air supplied at the periods of lack or low flow rate of the flue gases is also known. Due to the time averaging of hydrocarbon inflow rate the process enables to significantly reduce the size of a purification plant (adsorbers) . However in a longer time, the whole amount of hydrocarbons con- tained in flue gases are finally directed to adsorbers in this embodiment .
  • the invention aims on overcoming these disadvantages by providing an absorption-distillation section upstream the adsorption-desorption section and utilizing the negative pressure of the vacuum pump to provide a direct vacuum evaporation (distillation) of the light hydrocarbons from the adsorbent in the pe- riods of lower efficiency of hydrocarbon desorption from activated carbon.
  • the process of purification of flue gases from hydrocarbons comprises subjecting the gases to the absorption-distillation process utilising the negative pres- sure present in the adsorption-desorption section, before directing the gases to carbon adsorbers.
  • the process is characterised in that purified flue gases are directed to an absorption column, where they are contacted with absorbent comprising a mixture of hydrocarbons at an initial boiling point above 100°C and partially saturated with light hydrocarbons.
  • An absorbent flow rate is fixed and depends on absorbent temperature and desired hydrocarbon concentration in gases directed from an absorption column to an adsorber. The absorption of a significant part of hydrocarbons from the flue gases takes place in the column.
  • a gaseous mixture from the absorption column is directed to a carbon adsorber, and a spent absorption solution is directed to a distillation column, where a vacuum distillation of light hydrocarbons takes place under the pressure of from 2,5 kPa to 10 kPa.
  • the absorbent tempera- ture ranges from 1°C to 10°C in the absorption process and from 5°C to 20°C in the distillation process.
  • the adsorbers the adsorption of remaining hydrocarbons from a gaseous mixture or the vacuum desorption of the same hydrocarbons under the influence of the negative pressure generated by a vacuum system, are carried out alternately.
  • the purified gases are discharged from the adsorbers to the atmospheric air and the hydrocarbons are recovered through the vacuum system and directed to a hydrocarbon recovery section, namely to reabsorption in gasoline or condensation section.
  • the present process provides also, due to introducing of the pure air to absorption column, an additional desorption of hydrocarbons contained in the absorbent followed by recycling them to the gaseous volume of storage tanks, if only a pressure in this volume falls below the prescribed value.
  • the process of the invention permits to lower the amount and to desirably stabilise hydrocarbon concentration in gases directed to adsorbers (that in turn enables to optimise their values and decreases the hazard of self-ignition) , to fully utilise vacuum pomp yield and economise the energy delivered to the plant, by providing processes (of absorption and vacuum distillation) with opposite energetic effects.
  • Fig. 1 illustrates a schematic diagram of the process of purification from hydrocarbons of flue gases originating from the hermetization of petroleum products storage and distribution processes.
  • Fig. 1 illustrates a schematic diagram of the process of purification from hydrocarbons of flue gases originating from the hermetization of petroleum products storage and distribution processes.
  • the flue gases a from the hermetization of tank cars loading and storage tanks pouring with petroleum products in an amount up to 1600 rn ⁇ /h and a hydrocarbon content up to 2000 g/m ⁇ , are directed to a chamber A of an absorbent tank 1_, then are passed through an absorption column 2 placed on the chamber A, where they are contacted countercurrently with a spraying absorbent b at the temperature of about 5°C, whereby the absorbent b (the mixture of higher hydrocarbons of the initial boiling point above 100°C) is saturated with the light hydrocarbons contained in the gases a.
  • the absorbent b from the chamber B of an absorbent tank 1 is pumped through a cooler 5 by a pump 6 to the column 2 with the constant rate of about 14 m ⁇ /h.
  • a spent absorption solution j flows down to the chamber A of an absorbent tank 1 , while hydrocarbon depleted gases c with the hydrocarbon content up to 350 g/m ⁇ are directed to the one of the two alternately functioning adsorbers 1_ with activated carbon, from which in the adsorption cycle the purified air e is collected, and in the desorption cycle the recovered light hydrocarbons d are collected through the vacuum system _8.
  • vacuum distillation of hydrocarbons f in adsorber 1_ is carried out under the pressure of from 3,5 kPa to 8,0 kPa from absorbent c[ in an distillation column 4_ situated on the chamber B of an absorbent tank 1_.
  • the absorbent g_ in the temperature of about 12 °C for spraying in the column _ is passed from the chamber A of the tank 1 with the help of the pump 3 , and next after the distilla- tion it flows down to the chamber B of the tank 1, while the distilled hydrocarbons f are recovered through the vacuum system 8_.
  • the hydrocarbons h recovered from the desorption in adsorbers 2 and the distillation in the column 4_ are directed to the hydrocarbon recovery section _9.
  • the pure air p_ may be directed to the chamber A of an absorbent tank 1 , which on flow through the absorption column 2 desorbs additionally the hydrocarbons contained in the absorbent b, and a mixture k of the air and desorbed hydrocarbons is recycled to the gaseous volume of storage tanks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

A process of purification of gases from hydrocarbons, particularly gases such as a flue gas originating from the hermetization of petroleum products storage and distribution processes, utilising the absorption-adsorption process: the flue gases (a) are subjected to an absorption-distillation process comprising absorbing the light hydrocarbons contained in gases (a) an absorption column (2) by absorbent (b) being a mixture of the hydrocarbons followed by subjecting the light hydrocarbon saturated absorbent (g) to a vacuum distillation process in a distillation column (4), and subjecting the light hydrocarbon lean gases (c) leaving the column (2) alternately to an adsorption and vacuum desorption process in adsorbers (7), said light hydrocarbons (d) desorbed from adsorbers (7) and light hydrocarbons (f) distilled off the column (4) through the vacuum system (8) are directed to the hydrocarbon recovery section (9). In periods of negative pressure in the gaseous volume of storage tanks, pure air or another inert gas (p) is introduced to the absorption column (2) to desorb the light hydrocarbons contained in the absorbent (b).

Description

PROCESS FOR SEPARATING HYDROCARBONS FROM GASES, IN PARTICULAR GASES ORIGINATING FROM PETROLEUM STORAGE AND DISTRIBUTION
Background of the invention The present invention relates to the process of purification of gases from hydrocarbons, particularly gases such as a flue gas originating from the hermetization of petroleum products storage and distribution processes, which gases (vapours) comprise a mixture of hydrocarbons, especially C3 to Cg hydrocarbons, with air or another inert gas.
Several methods for purification of air or another inert gas originating from the hermetization of petroleum products storage and distribution processes are known. An adsorption-desorption process using an activated carbon with recovery of hydrocarbons contained in a flue gas being purified is used particularly frequently. A plant for the implementation of the process comprises an adsorption-desorption section, or carbon adsorbers with a vacuum system, and a hydrocarbon recovery section.
A basic disadvantage of the above solution is the necessity to direct all hydrocarbons contained in the flue gas stream to the carbon adsorbers and consequently to use a correspondingly large adsorbent bed.
A process (Patent Application P 336872) for stabilisation of hydrocarbon content and a flow rate of gases directed to a purification plant for purifying them from hydrocarbons, comprising subjecting the gases to an adsorption-desorption process on a column in a presence of air supplied at the periods of lack or low flow rate of the flue gases is also known. Due to the time averaging of hydrocarbon inflow rate the process enables to significantly reduce the size of a purification plant (adsorbers) . However in a longer time, the whole amount of hydrocarbons con- tained in flue gases are finally directed to adsorbers in this embodiment . All the above-described processes share a disadvantage of incomplete utilisation of a vacuum pump, as its full yield is used only in a relatively short initial period of hydrocarbon desorption from the adsorber. In subsequent periods the pump, though supplied with the same amount of energy, works with a dramatically decreased yield because of a decreasing amount of desorbed hydrocarbons (some cavitation may then also take place) .
Summary of the invention The invention aims on overcoming these disadvantages by providing an absorption-distillation section upstream the adsorption-desorption section and utilizing the negative pressure of the vacuum pump to provide a direct vacuum evaporation (distillation) of the light hydrocarbons from the adsorbent in the pe- riods of lower efficiency of hydrocarbon desorption from activated carbon.
According to the invention the process of purification of flue gases from hydrocarbons comprises subjecting the gases to the absorption-distillation process utilising the negative pres- sure present in the adsorption-desorption section, before directing the gases to carbon adsorbers.
The process is characterised in that purified flue gases are directed to an absorption column, where they are contacted with absorbent comprising a mixture of hydrocarbons at an initial boiling point above 100°C and partially saturated with light hydrocarbons. An absorbent flow rate is fixed and depends on absorbent temperature and desired hydrocarbon concentration in gases directed from an absorption column to an adsorber. The absorption of a significant part of hydrocarbons from the flue gases takes place in the column. A gaseous mixture from the absorption column is directed to a carbon adsorber, and a spent absorption solution is directed to a distillation column, where a vacuum distillation of light hydrocarbons takes place under the pressure of from 2,5 kPa to 10 kPa. The absorbent tempera- ture ranges from 1°C to 10°C in the absorption process and from 5°C to 20°C in the distillation process. In the adsorbers, the adsorption of remaining hydrocarbons from a gaseous mixture or the vacuum desorption of the same hydrocarbons under the influence of the negative pressure generated by a vacuum system, are carried out alternately. The purified gases are discharged from the adsorbers to the atmospheric air and the hydrocarbons are recovered through the vacuum system and directed to a hydrocarbon recovery section, namely to reabsorption in gasoline or condensation section. In periods of a low yield of hydrocarbon desorption from the adsorber, the process of distillation of the hydrocarbons previously absorbed on the absorbent proceeds in the distillation column due to the negative pressure, and these hydrocarbons are also directed to a hydrocarbon recovery section through the vac- uum system, bypassing the adsorbers.
The present process provides also, due to introducing of the pure air to absorption column, an additional desorption of hydrocarbons contained in the absorbent followed by recycling them to the gaseous volume of storage tanks, if only a pressure in this volume falls below the prescribed value.
The process of the invention permits to lower the amount and to desirably stabilise hydrocarbon concentration in gases directed to adsorbers (that in turn enables to optimise their values and decreases the hazard of self-ignition) , to fully utilise vacuum pomp yield and economise the energy delivered to the plant, by providing processes (of absorption and vacuum distillation) with opposite energetic effects.
The process according to the invention is further illustrated by an embodiment example and the drawing, wherein Fig. 1 illustrates a schematic diagram of the process of purification from hydrocarbons of flue gases originating from the hermetization of petroleum products storage and distribution processes. The best mode of carrying the invention Example. The flue gases a from the hermetization of tank cars loading and storage tanks pouring with petroleum products in an amount up to 1600 rn^/h and a hydrocarbon content up to 2000 g/m^, are directed to a chamber A of an absorbent tank 1_, then are passed through an absorption column 2 placed on the chamber A, where they are contacted countercurrently with a spraying absorbent b at the temperature of about 5°C, whereby the absorbent b (the mixture of higher hydrocarbons of the initial boiling point above 100°C) is saturated with the light hydrocarbons contained in the gases a. The absorbent b from the chamber B of an absorbent tank 1 is pumped through a cooler 5 by a pump 6 to the column 2 with the constant rate of about 14 m^/h. A spent absorption solution j flows down to the chamber A of an absorbent tank 1 , while hydrocarbon depleted gases c with the hydrocarbon content up to 350 g/m^ are directed to the one of the two alternately functioning adsorbers 1_ with activated carbon, from which in the adsorption cycle the purified air e is collected, and in the desorption cycle the recovered light hydrocarbons d are collected through the vacuum system _8. In the period of low efficiency of desorption process, vacuum distillation of hydrocarbons f in adsorber 1_ is carried out under the pressure of from 3,5 kPa to 8,0 kPa from absorbent c[ in an distillation column 4_ situated on the chamber B of an absorbent tank 1_. The absorbent g_ in the temperature of about 12 °C for spraying in the column _ is passed from the chamber A of the tank 1 with the help of the pump 3 , and next after the distilla- tion it flows down to the chamber B of the tank 1, while the distilled hydrocarbons f are recovered through the vacuum system 8_. The hydrocarbons h recovered from the desorption in adsorbers 2 and the distillation in the column 4_ are directed to the hydrocarbon recovery section _9. In periods of lowering the pres- sure in the hermetization network to below 100,5 kPa, the pure air p_ may be directed to the chamber A of an absorbent tank 1 , which on flow through the absorption column 2 desorbs additionally the hydrocarbons contained in the absorbent b, and a mixture k of the air and desorbed hydrocarbons is recycled to the gaseous volume of storage tanks.

Claims

Patent claims:
1. A process of purification of gases from hydrocarbons, particularly gases such as a flue gas originating from the her- metization of petroleum products storage and distribution processes, utilising the absorption-adsorption process, characterised in that the flue gases (a) before being directed to the adsorbers ( ) are subjected to the absorption-distillation process comprising absorbing the light hydrocarbons contained in gases (a) at the concentration above 350 g/m^ in the absorption column (2) by the absorbent (b) being a mixture of the hydrocarbons of the initial boiling point above 100°C, followed by subjecting the light hydrocarbon saturated absorbent (cj) , in the period of low efficiency of hydrocarbon desorption from adsorber (2) . to the vacuum distillation process in the distillation column (4.) , and subjecting the light hydrocarbon lean gases (c) leaving the column ( 2 ) alternately to the adsorption and vacuum desorption process in adsorbers (2) r said light hydrocarbons (d) desorbed from adsorbers (2) and light hydrocarbons (f) distilled off the column (4.) through the vacuum system (_8) are directed to the hydrocarbon recovery section (_9) .
2. The process according to claim 1 characterised in that the additional recovery of light hydrocarbons from absorbent (b) is carried out by the desorption with the pure air or another inert gas (p_) in the absorption column ( 2 ) , and said mixture (k) of air and desorbed hydrocarbons is recycled to the gaseous volume of storage tanks.
3. The process according to claim 1 characterised in that the temperature of the absorbent (b) used in the absorption col- umn (2) ranges from 1°C to 10°C, preferably 5°C, and the temperature of the absorbent (cj) subjected to the distillation ranges from 5°C to 20°C, preferably 12°C, and the distillation pressure ranges from 2,5 kPa to 10 kPa, preferably 3,5 kPa.
PCT/PL2000/000104 2000-03-24 2000-12-19 Process for separating hydrocarbons from gases, in particular gases originating from petroleum storage and distribution WO2001072400A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20319/01A AU2031901A (en) 2000-03-24 2000-12-19 Process for separating hydrocarbons from gases, in particular gases originating from petroleum storage and distribution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.339200 2000-03-24
PL339200A PL193894B1 (en) 2000-03-24 2000-03-24 Method of purifying gaseous substances evolving from hydrocarbons, in particular those to be discharged into atmosphere from hermetically enclosed petroleum products storage and distribution facilities

Publications (1)

Publication Number Publication Date
WO2001072400A1 true WO2001072400A1 (en) 2001-10-04

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PCT/PL2000/000104 WO2001072400A1 (en) 2000-03-24 2000-12-19 Process for separating hydrocarbons from gases, in particular gases originating from petroleum storage and distribution

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AU (1) AU2031901A (en)
PL (1) PL193894B1 (en)
WO (1) WO2001072400A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227891A (en) * 1979-01-29 1980-10-14 Youngstown Sheet And Tube Company Recovery of hydrocarbon vapors from air
US4715868A (en) * 1985-07-01 1987-12-29 Mcgill Incorporated Vapor recovery system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227891A (en) * 1979-01-29 1980-10-14 Youngstown Sheet And Tube Company Recovery of hydrocarbon vapors from air
US4715868A (en) * 1985-07-01 1987-12-29 Mcgill Incorporated Vapor recovery system

Also Published As

Publication number Publication date
AU2031901A (en) 2001-10-08
PL193894B1 (en) 2007-03-30
PL339200A1 (en) 2001-10-08

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