EP0230146B1 - Entschwefelung - Google Patents

Entschwefelung Download PDF

Info

Publication number
EP0230146B1
EP0230146B1 EP19860310206 EP86310206A EP0230146B1 EP 0230146 B1 EP0230146 B1 EP 0230146B1 EP 19860310206 EP19860310206 EP 19860310206 EP 86310206 A EP86310206 A EP 86310206A EP 0230146 B1 EP0230146 B1 EP 0230146B1
Authority
EP
European Patent Office
Prior art keywords
temperature
bed
absorbent
molecular sieve
feedstock
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.)
Expired - Lifetime
Application number
EP19860310206
Other languages
English (en)
French (fr)
Other versions
EP0230146A3 (en
EP0230146A2 (de
Inventor
Patrick John Denny
Peter John Herbert Carnell
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0230146A2 publication Critical patent/EP0230146A2/de
Publication of EP0230146A3 publication Critical patent/EP0230146A3/en
Application granted granted Critical
Publication of EP0230146B1 publication Critical patent/EP0230146B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents

Definitions

  • This invention relates to desulphurisation of feedstocks such as natural gas, or gases derived therefrom, and liquids or gases derived from oil or solid hydrocarbonaceous materials such as coal.
  • feedstocks such as natural gas, or gases derived therefrom, and liquids or gases derived from oil or solid hydrocarbonaceous materials such as coal.
  • Liquid feedstocks include LPG, naphthas, and kerosene.
  • Desulphurisation of such feedstocks can be effected by passing the gas through a suitable absorbent which is commonly zinc oxide and/or copper oxide and is typically in the form of granules or pellets.
  • a suitable absorbent which is commonly zinc oxide and/or copper oxide and is typically in the form of granules or pellets.
  • the present invention provides a method of desulphurising a liquid or gaseous feedstock wherein the feedstock is passed through a bed of a desulphurising absorbent characterised by temporarily increasing the temperature of the absorbent bed from the normal operating temperature by at least 50°C to a temperature not in an excess of 500°C, preferably not in an excess of 400°C.
  • the increase in temperature is preferably to a temperature in the range 150 to 350°C and is preferably for a period of at least 1 hour. While benefits are obtained by the use of extended periods, e.g. 1 or more days, at the increased temperature, at increased temperatures above about 280°C, the higher the temperature, the shorter should be the time at that temperature, in order to avoid undue loss of surface area of the absorbent.
  • the maximum temperature is preferably below 300°C.
  • the maximum normal operating temperature, at which there is a noticeable benefit by temporary increase of the temperature, is about 300°C: with the aforesaid high surface area absorbents the normal operating temperature is preferably below 250°C and is preferably in the range 0 to 150°C.
  • the absorbent bed may be subjected to the temperature increase while on-line if the resultant increase in temperature of the desulphurised product is acceptable: however such a process also involves heating of the feedstock during at least part of the period of the increased temperature and economic considerations may render this an unacceptable mode of operation.
  • the absorbent bed is heated while the bed is off-line.
  • two or more absorbent beds may be provided and while one or more beds remain on absorption duty one or more other beds are subjected to the temperature increase.
  • the bed may be heated via an external jacket, or by passing hot gas or liquid through the bed, until the desired maximum temperature has been achieved for a sufficient period and then the bed left static to cool down to the normal operating temperature.
  • desulphurisation follows treatment of the feedstock with a molecular sieve to adsorb other impurities e.g. moisture.
  • the molecular sieve adsorbent and the desulphurisation absorbent may be in the same vessel.
  • regeneration of the molecular sieve adsorbent is effected by heating
  • the temporary heating of the desulphurisation absorbent may be effected at the same time as regeneration of the molecular sieve adsorbent.
  • the regeneration of the molecular sieve and the temporary increase in temperature of the absorbent bed are effected by passage of a heated gas stream containing a combustible gas through the absorbent bed and through the molecular sieve.
  • the gas stream is combusted and the combustion products thereof are passed through a heat exchanger wherein heat is transferred to the gas stream employed for the regeneration step.
  • the time interval before the temporary heating of the desulphurisation absorbent becomes necessary will depend on the rate at which the absorbent becomes saturated, i.e. upon the absorbable sulphur compound content of the feedstock and the space velocity at which the feedstock is fed through the bed. Where the rate of sulphur pick up is very low, e.g. where the absorbable sulphur compounds content of the feedstock, and the space velocity, are low, little benefit may be obtained by the present invention. However such conditions are not normally encountered in commercial operations.
  • the heating step should normally be effected before the sulphur break-through becomes significant.
  • the number of heating steps that can be employed before the bed needs recharging will depend on how saturated the bed is before each heating step and the severity, i.e. duration and temperature of the heat treatment. After a number of heat treat­ments, which may be as few as one, economic considerations may indicate that recharging is preferable to a further temporary temperature increase.
  • the sulphur compounds initially present usually include one or more of the following: H2S, COS, and possibly CS2, CH3SH and others such as diethyl sulphide or tetramethylene sulphide.
  • the total initial concentration thereof is typically in the range 1-1000 ppm v/v calculated as sulphur-equivalent H2S.
  • the outlet sulphur compounds concentration is typically under 1 ppm, for example under 0.5 ppm, but this is a matter of design depending on the product user's requirement.
  • the absorbent material preferably comprises at least 60, especially at least 80, % w/w of ZnO, calculated on its con­stituents non-volatile at 900°C.
  • the zinc oxide may be, at least initially, wholly or partly hydrated or in the form of a salt of a weak acid.
  • the surface area of the solid material is at least 20, preferably in the range 50 to 200, m2g -1 ; and its pore volume is typically at least 0.2.
  • a preferred solid material for the process is characterised further by an H2S-adsorption capacity of at least 20, especially 35-80%, of the theoretical, at temperatures up to 120°C, as determined in a standard test in which a mixture of H2S (2000 ppm v/v), CO2 (4% v/v) and methane (balance) is passed over the solid material as 1 bar abs. pressure and a volume hourly space velocity of 1000.
  • the absorbent bed can be in the form of a fixed, lift­able or fluidised bed.
  • the absorbent comprised a bed of 60 ml of granules (of 3-5 mm diameter) of zinc oxide of surface are a 79 m2.g -1 inside a tube of 25 mm internal diameter and a mixture of natural gas, to which 5% v/v of hydrogen sulphide had been added, was used as the feedstock.
  • the feedstock was passed through the bed at 20°C and at a space velocity of 700 hr -1 at atmospheric pressure. Break-through of H2S occurred 93 minutes after commencing the gas flow. Calculation showed that at this stage the average sulphur content of bed was 8.6% w /w. Analysis confirmed this figure.
  • the gas flow was then stopped and, while still under a static atmosphere of the gas, the bed was heated to 200°C for 6 hours and then allowed to cool to 20°C.
  • the gas flow was stopped and residual gas flushed out with nitrogen.
  • the bed was then heated to 200°C under a static nitrogen atmosphere for 16 hours and then allowed to cool to 20°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (7)

1. Verfahren zur Entschwefelung eines flüssigen oder gasför­migen Einsatzmaterials, bei dem das Einsatzmaterial durch ein Bett aus einem Entschwefelungs-Absorptionsmittel hindurchgehen gelassen wird, dadurch gekennzeichnet, daß die Temperatur des Absorptionsmit­telbettes vorübergehend von der normalen Betriebstemperatur um wenigstens 50°C auf eine Temperatur von höchstens 500°C er­höht wird.
2. Verfahren nach Anspruch 1, bei dem die Temperatur für einen Zeitraum von wenigstens 1 h auf eine Temperatur im Bereich von 150 bis 350°C erhöht wird.
3. Verfahren nach Anspruch 1 oder Anspruch 2, bei dem das Ab­sorptionsmittel Zinkoxid und/oder Kupferoxid enthält und eine spezifische Oberfläche von mehr als 20 m².g-1 hat, wobei die normale Betriebstemperatur im Bereich von -10 bis +200°C und die maximale Temperatur unter 300°C liegt.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem das Ab­sorptionsmittel Zinkoxid und/oder Kupferoxid enthält und eine spezifische Oberfläche von mehr als 20 m².g-1 hat, wobei die normale Betriebstemperatur im Bereich von 0 bis 150°C liegt.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem wenig­stens zwei Absorptionsmittelbetten eingesetzt werden und, wäh­rend sich wenigstens ein Bett im Absorptionsbetrieb befindet, wenigstens ein anderes der Betten der Temperaturerhöhung unter­zogen wird und dann das wenigstens eine Bett, das der Tempera­turerhöhung unterzogen worden ist, in den Absorptionsbetrieb zu­rückgebracht wird.
6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem das Ein­satzmaterial auch mit einem Molekularsieb behandelt wird und das Molekularsieb durch Erhitzen regeneriert wird, wobei die Regenerierung des Molekularsiebs zu derselben Zeit wie die vor­übergehende Erhöhung der Temperatur des Absorptionsmittelbettes durchgeführt wird.
7. Verfahren nach Anspruch 6, bei dem sich das Molekularsieb und das Absorptionsmittelbett in demselben Behälter befinden.
EP19860310206 1986-01-10 1986-12-30 Entschwefelung Expired - Lifetime EP0230146B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8600574 1986-01-10
GB868600574A GB8600574D0 (en) 1986-01-10 1986-01-10 Desulphurisation

Publications (3)

Publication Number Publication Date
EP0230146A2 EP0230146A2 (de) 1987-07-29
EP0230146A3 EP0230146A3 (en) 1989-01-18
EP0230146B1 true EP0230146B1 (de) 1991-03-06

Family

ID=10591191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860310206 Expired - Lifetime EP0230146B1 (de) 1986-01-10 1986-12-30 Entschwefelung

Country Status (6)

Country Link
EP (1) EP0230146B1 (de)
JP (1) JPH0644971B2 (de)
CA (1) CA1299341C (de)
DE (1) DE3677945D1 (de)
GB (1) GB8600574D0 (de)
NO (1) NO168837C (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0262849B1 (de) * 1986-10-01 1992-07-29 Imperial Chemical Industries Plc Entschwefelung
GB8805351D0 (en) * 1988-03-07 1988-04-07 Ici Plc Desulphurisation
US7655135B2 (en) 2006-03-14 2010-02-02 Syntroleum Corporation Process for removing solid particles from a hydroprocessing feed

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313722A (en) * 1964-03-04 1967-04-11 Universal Oil Prod Co Continuous thermal diffusion process employing fixed beds of adsorbent and moving inlets and outlets
US4204947A (en) * 1978-04-03 1980-05-27 Chevron Research Company Process for the removal of thiols from hydrocarbon oils
US4224191A (en) * 1979-03-05 1980-09-23 Chevron Research Company High-copper-level comulled sulfur sorbent

Also Published As

Publication number Publication date
JPS62183833A (ja) 1987-08-12
CA1299341C (en) 1992-04-28
EP0230146A3 (en) 1989-01-18
DE3677945D1 (de) 1991-04-11
JPH0644971B2 (ja) 1994-06-15
NO870100D0 (no) 1987-01-09
NO168837C (no) 1992-04-08
NO168837B (no) 1991-12-30
NO870100L (no) 1987-07-13
GB8600574D0 (en) 1986-02-19
EP0230146A2 (de) 1987-07-29

Similar Documents

Publication Publication Date Title
US4865826A (en) Desulphurization
US4533529A (en) Sulfur recovery process
US3974256A (en) Sulfide removal process
US2952611A (en) Regenerative platinum catalyst reforming
AU615032B2 (en) Desulphurisation
US3620969A (en) Desulfurization by selective adsorption with a crystalline zeolitic molecular sieve
US5053209A (en) Removal of mercury from natural gas and liquid hydrocarbons utilizing silver on alumina adsorbent
JPH07504214A (ja) 改質触媒を保護するために硫黄を極限まで除去する方法
US4831207A (en) Chemical processing with an operational step sensitive to a feedstream component
US4709117A (en) Total isomerization process and apparatus
NO172696B (no) Fremgangsmaate for fjerning av svovelforbindelser fra et fluidraastoff
GB2072525A (en) Process for the removal of acid gases from a gas mixture mainly consisting of methane
US4605812A (en) Process for removal of arsenic from gases
US4983365A (en) Desulphurization
US5169516A (en) Removal of arsenic compounds from light hydrocarbon streams
US4175928A (en) Hydrodesulfurization purification process for coal gasification
US5164076A (en) Process for the adsorption of hydrogen sulfide with clinoptilolite molecular sieves
EP0332324B1 (de) Entschwefelung
EP0230146B1 (de) Entschwefelung
US4849202A (en) Sulfur recovery process using metal oxide absorbent with reducing gas purge
US4871521A (en) Sulfur recovery process using metal oxide absorbent with improved purge
EP0171451A1 (de) Verfahren zur Trennung von n-Paraffinen/Isoparaffinen bei dem das rezyklierte Verdrängungsgas gewaschen wird
EP0262849B1 (de) Entschwefelung
US4769229A (en) Sulfur recovery process using metal oxide absorber feed for regeneration
US4954331A (en) Sulfur recovery process using metal oxide absorbent

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19890307

17Q First examination report despatched

Effective date: 19900215

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3677945

Country of ref document: DE

Date of ref document: 19910411

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20001113

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20001120

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20001122

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20001123

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001218

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011231

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: IMPERIAL CHEMICAL INDUSTRIES P.L.C.

Effective date: 20011231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020702

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20011230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020830

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: GB

Ref legal event code: 728V

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: GB

Ref legal event code: 7282

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051230