EP0254781A1 - Méthode d'élimination de soufre dans une charge hydrocarbonée - Google Patents

Méthode d'élimination de soufre dans une charge hydrocarbonée Download PDF

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Publication number
EP0254781A1
EP0254781A1 EP86305801A EP86305801A EP0254781A1 EP 0254781 A1 EP0254781 A1 EP 0254781A1 EP 86305801 A EP86305801 A EP 86305801A EP 86305801 A EP86305801 A EP 86305801A EP 0254781 A1 EP0254781 A1 EP 0254781A1
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EP
European Patent Office
Prior art keywords
sulfur
sorbent
sulfur sorbent
inorganic oxide
group
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.)
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Application number
EP86305801A
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German (de)
English (en)
Inventor
Leslie A. Field
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.)
Chevron USA Inc
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Chevron Research and Technology Co
Chevron Research Co
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Publication date
Priority to ZA864295A priority Critical patent/ZA864295B/xx
Priority to JP61146772A priority patent/JPS633091A/ja
Application filed by Chevron Research and Technology Co, Chevron Research Co filed Critical Chevron Research and Technology Co
Priority to EP86305801A priority patent/EP0254781A1/fr
Publication of EP0254781A1 publication Critical patent/EP0254781A1/fr
Withdrawn legal-status Critical Current

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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
    • C10G61/06—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being a sorption process

Definitions

  • This invention relates to a method of removing sulfur compounds from the hydrocarbon feedstreams to a catalytic reformer.
  • Catalytic reforming processes play an integral role in upgrading naphtha feedstocks to high octane gasoline blend stocks. These processes have become more important in recent years because of the increase in demand for low-lead and unleaded gasolines.
  • the naph­tha feed is passed over a promoted noble metal catalyst at a temperature in the range of 3l5°C to 595°C, a pressure in the range of from l atmosphere to 70 atmospheres, a liquid hourly space velocity (LHSV) in the range of .l to l0, and a hydrogen to hydrocarbon mole ratio in the range of l to l0. Variations in these conditions will depend in large measure upon the type of feed processed and the desired product octane level.
  • the sulfur con­tent of the feedstock must be minimized to prevent poison­ing of the reforming catalyst.
  • the feed will contain less than 2 to 5 parts per million by weight (ppm) of sulfur, since the presence of sulfur in the feed decreases both the activity and the selectivity of the catalyst.
  • ppm parts per million by weight
  • Sulfur sorbents can remove nearly all of the sulfur present in the feed at the high temperatures used in reforming.
  • One sulfur sorbent that is used at low temperatures is a metal or metal compound, such as copper, which is supported on a porous refractory inorganic oxide support or on a carbon support.
  • An example of such a sorbent is disclosed in U.S. Patent No. 4,204,947. That sorbent is copper supported on alumina.
  • Other similar sorbents are disclosed in U.S. Patent Nos. 2,593,464 and 4,224,l9l.
  • Copper on alumina works well as a sorbent for H2S or mercaptan type sulfur, but copper sorbents tend to be less effective at higher temperatures, removing less sulfur as the temperature goes above 300°C. Furthermore, copper sorbents do not work on some types of sulfur which can be present in the reforming feed, such as thiophenic sulfur. Also, copper is costly.
  • U.S. Patent No. 4,008,l74 discloses copper and chromium on a carbon support. The chromium aids in regeneration of the sorbent.
  • the present invention is a novel method of removing sulfur from hydrocarbon feedstreams by using a metal component containing a metal selected from Group I-A or Group II-A of the Periodic Table supported on a porous refractory inor­ganic oxide support.
  • Preferred metal components include sodium, potassium, calcium and barium.
  • Preferred refrac­tory inorganic oxide supports include alumina, silica, boria, titania, zirconia, aluminosilicates, aluminophosphates, and mixtures of two or more thereof.
  • One preferred method of making these sulfur sorbents is by impregnating a preformed porous refractory inorganic oxide support with an aqueous solution of a metal salt, where the metal is selected from Groups I-A or II-A of the Periodic Table, and drying and calcining the resulting material.
  • An alternative method is by peptizing a refrac­tory inorganic oxide support, thereby forming a plastic mass, mulling the mass with a compound containing a Group I-A or Group II-A metal, then extruding the mass, and drying and calcining it.
  • a refinery produces naphtha fractions having substantial amounts of sulfur in the form of organic sul­fides, such as thiophenes and mercaptans.
  • the sulfur level is higher than l00 ppm in the untreated naph­tha fraction.
  • These feeds with very high sulfur levels can be contacted with hydroprocessing catalysts to convert the sulfur compounds to H2S. If the remaining sulfur level is too high, then the high sulfur level can cause the reforming catalyst to rapidly lose both activity and selectivity when used for reforming. Prudent operation demands that heavily sulfur contaminated feeds be further treated before contacting sulfur sensitive catalysts.
  • Preferred supports for the sulfur sorbent include alumina, silica, titania, zirconia, boria, and the like, and mixtures thereof. Clays can also be used as supports. Particular clays of interest include the fibrous magnesium silicate clays, for example, attapul­gite, halloysite, palygorskite and sepiolite.
  • the support can be premade by any method known in the art.
  • the surface area of the finished sulfur sorbent is in large part due to the support chosen. It is believed that the active sulfur sorbents of this invention can have nitrogen surface areas in the range of between 20 and 300 m2/g.
  • one typical feedstock will be low molecular weight hydrocarbons which are in the vapor phase at reforming conditions.
  • the feedstock will normally comprise alkanes and naphthenic compounds having between about five and twelve carbon atoms.
  • Hydrogen may also be present, such as the recycle hydrogen stream of a reform­ing unit. Because vapors diffuse rapidly into the pores of the support material, the precise size and pore dis­tributions are not thought to be critical in a sulfur sorbent for use in this application.
  • the metal components of the sulfur sorbents in this invention can be Group I-A or Group II-A metal con­taining compounds.
  • the preferred metal components are sodium, potassium, calcium, and barium.
  • the metal compo­nents are not in general present as the reduced metal. Instead, they are usually present in the form of a salt, oxide, hydroxide, nitrate, or other compound. It is the metal in the compound, in any form, that is the metal component of the sorbent of this invention.
  • the sulfur sorbents of this invention can be made by impregnation of a preformed refractory inorganic oxide support with a metal component, or by comulling the metal component with the inorganic oxide support.
  • Preferred metal compounds include sodium chlo­ride, sodium nitrate, sodium hydroxide, sodium carbonate, sodium oxalate, potassium chloride, potassium nitrate, potassium carbonate, potassium oxalate, potassium hydroxide, barium chloride, barium nitrate, barium carbonate, barium oxalate, barium hydroxide, calcium chlo­ride, calcium nitrate, calcium carbonate, calcium oxalate, calcium hydroxide, and the like.
  • a preformed inorganic support can be impregnated with Group I-A or Group II-A metals by standard tech­niques. It may be necessary to impregnate the support several times to achieve the desired amount of metal com­ponent on the inorganic support.
  • Various metal compounds can be dissolved to form aqueous solutions useful for this impregnation. The preferred compounds for impregnation are the more soluble compounds.
  • a compound should have a solubility of at least 0.l mole per liter of water.
  • Another method of making the sulfur sorbents of this invention is by mulling the powdered inorganic support material, which may be prepeptized or mixed in the presence of a peptizing agent, together with a compound containing a Group I-A or Group II-A metal.
  • Preferred peptizing agents are mineral acids, such as nitric acid.
  • peptized alumina powder could be mixed with a metal component, such as potassium carbonate. The result­ing mass is then extruded, dried and calcined to form the final sulfur sorbent.
  • the choice of the appropriate compound to use during fabrication of the sulfur sorbent is primarily dictated by the solubility of the salt. For example, in impregnation, very soluble salts are desired such as nitrates, but in mulling, relatively insoluble salts such as carbonates are preferred.
  • the sulfur sorbent of this invention include being commingled with or preferably preceded by small amounts of platinum or palladium, either on the sorbent or on a suitable support. Between 0.0l weight percent and 0.5 weight percent platinum or palla­dium may be added. In the presence of added hydrogen, the added metals catalyze the conversion thiophenic and other organic type sulfur compounds that may exist in the feed­stream into easily sorbed sulfur compounds. If the platinum or palladium is on the sorbent particles them­selves, it may also reduce coking of the feed on the sorbent particles. When thiophenic and other organic sulfur compounds contact platinum and palladium, hydrogen sulfide is formed, which is readily removed by the sulfur sorbent.
  • the sorbent of this invention is used to remove sulfur from feedstocks containing sulfur levels as high as several percent to levels as low as l ppm (part per mil­lion) and lower.
  • the sorbent and reforming catalyst are contained in separate vessels.
  • the vessel containing the sulfur sorbent is typically placed upstream of the vessel containing the reforming catalyst.
  • the feedstock may be heated to as high as the reforming reac­tion temperature or to a lower temperature before it con­tacts the sulfur sorbent; from ambient temperature to as high as l000°F (540°C) and higher.
  • the sorbent can be placed in the same reaction vessel as the reforming catalyst. If the sorbent is given the proper porosity and shape it can be inter-mixed with the reforming catalyst, in the same bed. As any residual organic sulfur is converted by the reforming catalyst to H2S, the sorbent removes it, preventing harm to subsequent beds, and prolonging operational life of the system because the sorbent functions well at reforming tempera­tures.
  • the sorbent can safely contact the amounts of water normally found in reforming feedstreams.
  • the feed­streams do not have to be as extraordinarily dry as they would if they were contacting the reduced, metallic form of alkali metals or alkaline earth metals and if this reduced, metallic form were required.
  • Group I-A and Group II-A metals can form hydroxides or oxides in a water-containing stream.
  • the water level in the hydrogen recycle stream should be kept low, preferably to less than l00 ppm, and more preferably to less than 50 ppm.
  • This sorbent can be used in combination with other sorbents.
  • the hydrocarbon feedstock is contacted with a hydrotreating catalyst to convert organic sulfur compounds in the feed­stock, then the feedstock is contacted with a sorbent, such as zinc oxide or copper oxide, supported on a clay base, then the feedstock is contacted with the sorbent of the present invention.
  • the preformed gamma alumina base used was a commercially available 1/16th inch (1.6 mm) extrudate, with a H2O pore volume of approximately .7 cc/gm and a N2 surface area of approximately 200 m2/gm. It was calcined at l250°F (677°C). It was made by peptizing a pseudoboehmite alumina of crystal size in the range of approximately 33 to 40 Angstroms as determined by X-ray diffraction (XRD) with an aqueous solution of a mineral acid, mixing it until it reached an extrudable state, then extruding, drying and calcining the resulting material.
  • XRD X-ray diffraction
  • This example shows a sulfur sorbent of this invention.
  • the sorbent was prepared by taking l00 gm of pre-extruded alumina and impregnating it with 25.9 gm KNO3 in 76 ml H2O, by pore fill impregnation. The sorbent was dried for l6 hours at 250°F (121°C) and then calcined for 2 hours at ll00°F (593°C). .12 ml of a solution of .093 gm Pt/ml, where the form of Pt was H2PtCl6, in distilled water was then impregnated onto the support. It was dried for 48 hours at 250°F (121°C) and calcined for 2 hours at 500°F (260°C). This composi­tion of matter will be identified as A.
  • This example shows another sulfur sorbent of this invention.
  • 200 grams of pre-extruded alumina were impregnated with .22 ml of .093 gm Pt/ml, where the form of Pt was H2PtCl6, in l64 ml H2O, under 30 inches (76.2 cm) of vacuum.
  • the extrudate was then impregnated with 57.43 grams of potassium nitrate in l64 ml of water.
  • the extrudate was dried at 250°F (121°C) overnight and then calcined for 2 hours at ll00°F (593°C). This composition of matter will be identified as B.
  • This example shows the manufacture of a mono­metallic reforming catalyst.
  • 50 grams of pre-extruded alumina was impregnated under 30 inches (76.2 cm) of vacuum with l.6 ml of an aqueous solution of H2PtCl6 of concentration .093 gm Pt/ml in 30 ml of H2O.
  • the impregnated alumina was allowed to stand for 2 hours and then dried at 250°F (121°C) overnight and then calcined for 2 hours at 950°F (510°C) in air.
  • the catalyst produced can be used for reforming. This composition of matter will be identified as C.
  • This example was a standard reforming run using a sulfur-sensitive reforming catalyst except that (l) there was no sulfur sorber; and (2) l ppm sulfur was added to the feed after 480 hours.
  • the catalyst in this example was D.
  • the results before and after sulfur addi­tion are shown in the following table. After 600 hours, control of temperature to maintain the required aromatics content was no longer possible due to rapid catalyst deac­tivation. After 670 hours, the addition of sulfur to the feed was discontinued, and clean feed was used. No recovery of activity was observed during 50 hours of clean feed operation. In addition, the feed was withdrawn at 720 hours, and the catalyst was stripped with sulfur-free hydrogen gas for 72 hours at 930°F (499°C). Only a small gain in activity was observed.
  • Deionized water was added to 0.23 ml of a solu­tion containing 0.093 gm Pt/ml, the Pt as H2PtC16. The water was added until the total volume of the solution was l70 ml. This mixture was used to vacuum impregnate 200 gm of a preformed alumina extrudate. The impregnated extrudate was then allowed to stand for 2 hours at room temperature, and was then dried for l6 hours at 250°F (121°C).
  • the solids were then dried at 250°F (121°C) over a week­end, and calcined for 16 hours at 1100°F (593°C) in flowing air.
  • This material will be designated G.
  • Figure l is a plot of the catalyst average tem­perature of the material G required to maintain the target refractive index of the C5+ liquid product of l.4300, which corresponds to about 47 wt% aromatics in the liquid.
  • the Pt containing material F in front of the sorbent material E serves to convert the thiophenic sulfur to H2S, a form readily sorbed by the material.

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP86305801A 1986-06-09 1986-07-29 Méthode d'élimination de soufre dans une charge hydrocarbonée Withdrawn EP0254781A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ZA864295A ZA864295B (fr) 1986-06-09 1986-06-09
JP61146772A JPS633091A (ja) 1986-06-09 1986-06-23 炭素供給流から硫黄を除去する方法
EP86305801A EP0254781A1 (fr) 1986-06-09 1986-07-29 Méthode d'élimination de soufre dans une charge hydrocarbonée

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA864295A ZA864295B (fr) 1986-06-09 1986-06-09
EP86305801A EP0254781A1 (fr) 1986-06-09 1986-07-29 Méthode d'élimination de soufre dans une charge hydrocarbonée

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EP0254781A1 true EP0254781A1 (fr) 1988-02-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311239A (zh) * 2016-07-21 2017-01-11 绍兴文理学院 一种高效凹凸棒石黏土基催化剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1760585A (en) * 1923-11-21 1930-05-27 Cross Dev Corp Process of refining hydrocarbons
US2951804A (en) * 1957-10-22 1960-09-06 Houdry Process Corp Purification of reformate charge stocks using activated alumina impregnated with alkali or alkaline earth metal hydroxides
SU622800A1 (ru) * 1976-12-21 1978-09-05 Всесоюзный научно-исследовательский институт углеводородного сырья Способ тонкой очистки углеводородов
WO1986002629A1 (fr) * 1984-10-31 1986-05-09 Chevron Research Company Systeme d'elimination du soufre pour proteger un catalyseur de reformation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1760585A (en) * 1923-11-21 1930-05-27 Cross Dev Corp Process of refining hydrocarbons
US2951804A (en) * 1957-10-22 1960-09-06 Houdry Process Corp Purification of reformate charge stocks using activated alumina impregnated with alkali or alkaline earth metal hydroxides
SU622800A1 (ru) * 1976-12-21 1978-09-05 Всесоюзный научно-исследовательский институт углеводородного сырья Способ тонкой очистки углеводородов
WO1986002629A1 (fr) * 1984-10-31 1986-05-09 Chevron Research Company Systeme d'elimination du soufre pour proteger un catalyseur de reformation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 89, no. 24, December 1978, page 154, abstract no. 200241d, Columbus, Ohio, US; & SU-A-622 800 (ALL-UNION SCIENTIFIC-RESEARCH INSTITUTE OF HYDROCARBON RAW MATERIALS) 05-09-1978 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311239A (zh) * 2016-07-21 2017-01-11 绍兴文理学院 一种高效凹凸棒石黏土基催化剂及其制备方法

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Publication number Publication date
JPS633091A (ja) 1988-01-08
ZA864295B (fr) 1986-12-08

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