EP0052096A1 - Separation du sulfure d'hydrogene de courants fluides - Google Patents

Separation du sulfure d'hydrogene de courants fluides

Info

Publication number
EP0052096A1
EP0052096A1 EP19800901641 EP80901641A EP0052096A1 EP 0052096 A1 EP0052096 A1 EP 0052096A1 EP 19800901641 EP19800901641 EP 19800901641 EP 80901641 A EP80901641 A EP 80901641A EP 0052096 A1 EP0052096 A1 EP 0052096A1
Authority
EP
European Patent Office
Prior art keywords
halide
tower
solution
tri
electrolytic cell
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.)
Withdrawn
Application number
EP19800901641
Other languages
German (de)
English (en)
Inventor
Calvin Keith Deem
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Combustion Engineering Inc
Original Assignee
Combustion Engineering Inc
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 Combustion Engineering Inc filed Critical Combustion Engineering Inc
Publication of EP0052096A1 publication Critical patent/EP0052096A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • 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
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • 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
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide

Definitions

  • the present invention relates to inhibiting the loss of the diatomic halogen associated with the tri-halide whose solution is flowed in contact with a fluid, from which is removed sulfur compounds, including hydrogen sulfide. More particularly, the inven ⁇ tion relates to the use of a spent iodide solution from the bottom of a contact tower to that point in the upper portion of the tower where the vaporizing iodine would be swept by a treated fluid from the tower and thereby lost.
  • the second of these two plants was built near Bakersfield, California, for Superior Oil Company. It has survived with continual operation.
  • the second plant was studied and found to have at least two problems in its operation.
  • the first of the problems is in loss of the iodide charge of the system.
  • the second problem is in the .: corrosion of the outlet conduit system from the contact zone.
  • the Superior system introduces the complex compound of iodine and potassium iodide in the contact zone so it will flow downward in contact with the gas being treated as it flows upward. A portion of the iodine of the weakly bonded-'- complex is swept into the discharge system of the treated gas. ' This loss of the iodine to the system is a significant operation cost.
  • the iodine swept into the discharge system is significantly corrosive.
  • the periodic replacement cost of the carbon steel conduit of the discharge system is an additive to the operation cost.
  • the present invention contemplates flowing spent halide solution to a point in the upper portion of the tower to absorb the volatile diatomic halogen of the reversible reaction of the tri-halide and control the reversible reaction of the tri-halide to inhibit the release of the diatomic halogen.
  • the present invention further contemplates the use of a solution of potassium tri-iodide to contact gases containing sulfur compounds, including hydrogen sulfide.
  • the resulting potassium iodide is routed to absorb volatile iodine released above the zone of contact between potassium tri-iodide and hydrogen sulfide and to control the release of iodine.
  • the single figure of drawing is a diagrammatic representation of the system for removing sulfur compounds from a gaseous stream and incorporating the present invention.
  • the electrolytic cell is exhaustively described in the incorporated disclosure.
  • the function of the cell need only be recognized here in its consumption of elec ⁇ trical energy.
  • the cell functions to convert the solution from a lower oxidizing state to a higher oxidizing state. More specifically, in the present disclosure, a selection of a halide for the preferred embodiment results in the halide being converted, in the cell, to a tri-halide and becoming in the oxidation process, a mono-halide of a lower oxidizing state.
  • a solution containing the tri-halide is flowed from the electrolytic cell in countercurrent flow with fluid to be treated.
  • a vertical tower is employed for this contact between fluids.
  • a portion of the spent, or mono-halide, is flowed from the lower portion of the contact tower and the elemental sulfur removed from the solution preparatory to the reconversion of the solution in the electrolytic cell.
  • the present disclosure is initiated with a more ' specific consideration of electrolytic cell 10.
  • the oxidizing material pro ⁇ symbolized by the electric power to cell 10 is passed in countercurrent flow to fluids containing sulfur compounds to be oxidized.
  • the countercurrent flow contact is carried out in vertical tower 13.
  • the spent solution is accumulated in the bottom of tower 13 and cycled back to electrolytic cell 10 for regeneration.
  • the elemental sulfur resulting from the oxidation pro ⁇ cess in tower 13 is mechanically removed from the cycle in flotation cell 19. This is a er simple, continuous cycle. If efficient, the cycle can operate with a minimum loss of its oxidizing material.
  • the fluids flowing through contact tower 13 will have their sulfur compounds stripped from them, down to a satis ⁇ factory minimum, and discharged from the process through conduit 15.
  • the halides in solution brought to their higher state of oxidation by cell 10 are in a reversible reaction.
  • the volatile diatomic halogen can be released from the solution if the reversible reaction is shifted to the right.
  • not all of the halide in its higher state is available for oxidation of the sulfu compounds.
  • electrolytic cell 10 is depicted as producing its output solution into conduit 11.
  • Surge tank 12 is disclosed in conduit 11 to provide for venting gases generated by the cell.
  • Downstream of surge tank 12 in conduit 11 is pump 12-A. It is this pump 12-A which delivers the tri-halide solution from the surge tank 12 to the upper portion of vertical tower 13 at the highest pressure of the system. This pressure is greater than that within tower 13 to flow the tri-halide solution into tower 13.
  • contact tower 13 The construction of contact tower 13 is conventional, having been described adequately in the incorporated disclosure. A series of horizontal trays are mounted therein down which the solution of output cell 10 i flowed in its contact with the sulfur compound-containing gas flowed upwardly.
  • Gaseous fluid containing sulfur compounds and hydrogen sulfide, are flowed up through tower 13.
  • a source of such gases is connected to conduit 14 which is connected as an input to the lower portion of tower 13.
  • the treated gaseous fluid is conducted from the upper portion of tower 13 and through conduit 15.
  • the spent treating fluid specifically a solution containing the mono-halide, is collected in the lower portion of tower 13 to be flowed therefrom through conduit 16.
  • Output conduit ' 16 has a valve .17 mounted therein across which any superat ospheric pressure of tower 13 is reduced. This pressure reduction on the treating solution is necessary for the ready removal of elemental sulfur in downstream separation apparatus.
  • the separation apparatus may consist of a separator vessel 18 and a gas flotation cell 19.
  • the flotation cell 19 may require close adjust ⁇ ment of the amount of gas evolved to efficiently flotate the elemental sulfur to be removed.
  • the separator vessel 18 forms a structure from which a portion of the gas may be evolved prior to evolvement in the flotation process. Final adjustment of the gas to be evolved in vessel 19 may be regulated by the adjustment of valve 18-A in the gas outlet of separator vessel 18.
  • valve 18-B in the connection between separators 18 and cell 19 is regulated to maintain the liquid level in separator 18 and give the final pressure drop to atmosphere in cell 19.
  • the solution remaining after sulfur removal is returned to cell 10 by way of conduit 20.
  • Motive power is supplied by pump 21.
  • the present invention contemplates absorbing the volatile diatomic halogen with a solution and keeping them cycled in the process by passing down tower 13. This absorbing material is introduced into the top of tower 13 at that point in the process which follows contact between the up-flowing gas being treated and the down-flowing solution from cell 10.
  • the present invention was reduced to. practice by the use of potassium iodide as the halide ofthe process.
  • the electrolytic cell 10 converted the potassium iodide to potassium tri-iodide and 5 this compound was the effective oxidizing agent introduced into tower 13 to treat the sulfur-containing gases.
  • reversibility of the reaction of the potassium tri-iodide in solution causes the release of some of the volatile iodine unless strongly driven to the left.
  • the volatile iodine is not absorbed readily in 10 water but is absorbed readily in a solution of potassium iodide.
  • the answer to the problem was to transport a solution of potassium iodide to the upper portion of vertical tower 13 to absorb the vola ⁇ tile-iodine.
  • Conduit 30 is shown as a conduit from the lower portion of tower 13 to that upper portion of tower 13 where the solution of 20 potassium iodide will most effectively absorb the volatile iodine • from the reversible reaction and shift the reversible reaction to the left.
  • All of the fluids moved through the system disclosed are 25 supplied power for movement by various pumps.
  • the gas being treated is applied through conduit 14 at a pressure which may or may not be supplied by a pump *
  • the pressure may be the native pressure of pro duction or that of a pump; it does not matter. It is generally assum • 30 that the pressure within tower 13 is substantially above atmospheric.
  • Valve 17 has been disclosed as reducing the pressure toward that value at which sulfur removal may be readily carried out from the spent solution drawn from the lower portion of tower 13. The pressure of this solution stream is then increased to that value 35 selected for the operation of cell 10. From cell 10, pump 12-A again increases the pressure to the value needed to inject the solution out of cell 10 into tower 13.
  • Valve 17 can and may well be controlled from a liquid level sensing device responsive to the level of the spent solution collected in the lower portion of tower 13. All of these arrange ⁇ ments for circulating the fluids of the system, reducing their pressure, and elevating their pressure are the conventional manipulation necessary for the fluid mechanics of the system.
  • the delivery of the absorbing solution to the upper portion of tower 13 is disclosed as through conduit 30.
  • a pump, or equivalent must be supplied to pick up the spent solution in the system between tower 13 and the entrance to pump 21 for delivery to the upper portion of tower 13.
  • Pump 31 is disclosed in conduit 30 for this purpose.
  • Another element of control relates to cell 10.
  • the electric power to cell 10 may be varied to obtain the desired concentration of the higher state of treating material supplied to the sulfur removal process of tower 13. Therefore, a colorimeter 32 is connected to respond to the concentrat on of treating material within tower 13 and develop a signal on line 33 which will adjust regulator 34 in varying the power from source 35 applied to cell 10.
  • the novelty in the arrangement is the discovery of the point in the process which can be sensed to vary the power applied to cell 10 to maintain the process at its predeter ⁇ mined set point. The mechanics of carrying out this control are straight forward.
  • the preferred embodiment of the invention utilizes potassium iodide to combine with selected sulfur compounds of the treated fluid, it should be understood that any of the ha! ides selected from the group consisting of potassium, bromide, sodium iodide, and sodium bromide will also be satisfactory under the concepts of the invention.
  • the solution in which these ha! ides are included may contain varying amounts of water and one of the glycols. This treating solu- tion is passed through the cell 10 with the object of converting the halides to tri-halides which will combine with the sulfur compounds in

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

Une solution liquide contenant un tri-halogenure du groupe des halogenes compose du brome et de l'iode circule a contre-courant dans des fluides contenant des composes de soufre, comprenant du sulfure d'hydrogene a l'interieur d'une tour (13). La solution de tri-halogenure extrait des composes de soufre selectionnes, comprenant l'halogenure d'hydrogene des fluides et la solution d'halogenure est drainee depuis le fond (16) de la tour (13) pour l'extraction du soufre, la regeneration electrolytique et la liberation d'hydrogene de sorte qu'un tri-halogenure provenant de la cellule electrolytique (10) peut etre renvoye a la tour pour l'extraction continuelle de composes de soufre, comprenant le sulfure d'hydrogene. Une partie de la solution d'halogenure utilisee est amenee (3) du fond de la tour a un point dans la tour au-dessus du point d'introduction de la solution de tri-halogenure de maniere a empecher la perte de l'halogene diatomique.
EP19800901641 1980-05-12 1980-05-12 Separation du sulfure d'hydrogene de courants fluides Withdrawn EP0052096A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1980/000561 WO1981003346A1 (fr) 1980-05-12 1980-05-12 Separation du sulfure d'hydrogene de courants fluides

Publications (1)

Publication Number Publication Date
EP0052096A1 true EP0052096A1 (fr) 1982-05-26

Family

ID=22154341

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800901641 Withdrawn EP0052096A1 (fr) 1980-05-12 1980-05-12 Separation du sulfure d'hydrogene de courants fluides

Country Status (2)

Country Link
EP (1) EP0052096A1 (fr)
WO (1) WO1981003346A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU85457A1 (de) * 1984-07-10 1985-09-12 Euratom Verfahren zur erzeugung von wasserstoff und schwefel aus schwefelwasserstoff und schwefelwasserstoff enthaltenden gasen
LU87923A1 (de) * 1991-04-24 1992-11-16 Euratom Verfahren zum entfernen von schwefelwasserstoff und/oder schwefelkohlenstoff aus abgasen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794668A (en) * 1928-05-01 1931-03-03 Warren F Bleecker Method for treating petroleum
US3401101A (en) * 1966-08-05 1968-09-10 Howard F. Keller Jr. Separation of hydrogen sulfide and mercaptans from fluid streams
US4220505A (en) * 1978-12-06 1980-09-02 Combustion Engineering, Inc. Separation of hydrogen sulfide from fluid streams

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8103346A1 *

Also Published As

Publication number Publication date
WO1981003346A1 (fr) 1981-11-26

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Inventor name: DEEM, CALVIN KEITH