EP0697454B1 - Säurebehandelte anorganische Formkörper und deren Verwendung - Google Patents
Säurebehandelte anorganische Formkörper und deren Verwendung Download PDFInfo
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- EP0697454B1 EP0697454B1 EP95112751A EP95112751A EP0697454B1 EP 0697454 B1 EP0697454 B1 EP 0697454B1 EP 95112751 A EP95112751 A EP 95112751A EP 95112751 A EP95112751 A EP 95112751A EP 0697454 B1 EP0697454 B1 EP 0697454B1
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- EP
- European Patent Office
- Prior art keywords
- acid
- use according
- mouldings
- loaded
- pore radius
- 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
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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
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Definitions
- the invention relates to the use of porous inorganic Shaped bodies that are loaded with acid are, for the removal of basic nitrogen compounds, especially of ammonia or basic nitrogen-hydrocarbon compounds from ammonia and / or hydrocarbonaceous Mixtures.
- ion exchanged resins in the H form are used in the refineries as adsorbents for removing nitrogenous basic compounds, such as pyridine, from xylene, lubricating oils or petroleum distillates, which are said to have a much higher adsorption capacity than clays.
- these resins have to be regenerated periodically with hydrochloric acid, which often poses a poisoning problem for downstream catalysts or a plant-specific corrosion problem. (Yan, TY; Shu, P., Ind. Eng. Chem. Res., 1987, 26, pp. 753-755).
- DE-A-41 40 455 describes abrasion-resistant and porous composite moldings known which is an inorganic highly porous filler material (e.g. Y zeolite in the H form) and a substantially contain carbon matrix material.
- the moldings are used as adsorbents for benzene vapors.
- AT-A-24 61 06 describes a method for producing a three-dimensional crystalline material known by Treatment of mordenite with a mineral acid is obtained.
- This material can be used as an adsorbent, u. a. for tributylamine, be used. However, it is not specified that the latter Is part of a hydrocarbon-containing mixture.
- EP-A-0 278 694 describes a process for the removal of basic nitrogen compounds from extracted oils under Use of acidic polar adsorbents and for regeneration of adsorbents known.
- acidic polar adsorbents For example, H-Y zeolites are used, based on their degree of acid loading nothing is said.
- FR-A-2 438 083 relates to a process for the removal of nitrogen-containing compounds in liquid hydrocarbons with the aid of a solid adsorbent, such as silica, bauxite, zeolites X and Y, aluminum oxide, silica / aluminum oxide, on which an anhydrous acidic gas is adsorbed.
- a solid adsorbent such as silica, bauxite, zeolites X and Y, aluminum oxide, silica / aluminum oxide, on which an anhydrous acidic gas is adsorbed.
- Anhydrous HCl is preferably used, and anhydrous SO 2 , SO 3 , HBr and H 2 S can also be used.
- a loading with water-containing acids is not specified.
- Industrial adsorbents are usually as shaped bodies used because these e.g. in fixed bed reactors at continuous Processes over powders have the advantage that they the currents to be treated have a lower flow resistance oppose. This is reflected in a technically drastic way reflected in a lower pressure drop. It is also on to ensure the lowest possible abrasion value of the moldings.
- the object of the invention was to remove substances of ammonia or basic nitrogen-hydrocarbon compounds from ammonia and / or hydrocarbonaceous To provide mixtures, on the one hand, a large adsorption capacity have and on the other hand a high abrasion resistance show under reaction conditions.
- the invention relates to the use of porous, inorganic Shaped bodies whose pores are loaded with 2 to 95% sulfuric acid, phosphoric acid or solid acids are to remove basic nitrogen compounds, especially of ammonia or basic nitrogen-hydrocarbon compounds, from ammonia and / or hydrocarbonaceous Mixtures.
- the basic nitrogen-hydrocarbon compounds preferably contain 1 to 20, especially 1 to 12 carbon atoms.
- the moldings used can generally be called “solid Acids "and include, for example, molded articles from non-porous carrier particles, in their intermediate grain volume Acid is included. Mixtures of inorganic carriers with solid acids, such as heteropolyacids, boric acid or organic Sulfonic acids are useful.
- the carbon content the shaped body is generally less than 2% by weight, in particular less than 1% by weight.
- the moldings are preferably made of porous substances, such as Silicas, layered silicates, clays, zeolites, titanium dioxide, Zirconia and their mixtures formed with are loaded with liquid or solid acids.
- the acid-laden porous molded articles are preferably two-layer or three-layer silicates used, which are preferably acid-activated.
- Two-layer silicates include kaolin.
- Three-layer silicates are, for example, montmorillonite, hectorite, 3, Jrlite, saponite, antigorite, vermicullite, etc.
- Others usable silicates are, for example, sepiolite and Attapulgite.
- the layer silicates containing montmorillonite are in particular the bentonite and the so-called "Fuller's Earth ". Because these minerals are of natural origin are, they can in the respective composition be different.
- silicas used according to the invention are amorphous chains, rings and branches Polysilicic acids.
- a special case for amorphous silicas are the diatomaceous earths that come from natural sediment deposits
- organic or inorganic binders such as starch, cellulose derivatives, clays, add hydraulic cements etc.
- Acid activation of the silicates is not absolutely necessary if the starting material has already been subjected to an acid treatment or if it already has a high pore volume and an acid surface.
- the H + form of the zeolites can be used without prior acid activation, since they already have a relatively wide pore structure.
- the average pore diameter of type ZSM5 zeolites is about 0.5 nm, for faujasite about 1 nm. Mixtures of non-acid-treated starting materials and solid or liquid acids are also possible.
- catalyst supports based on acid activated three layer silicates are used, e.g. the so-called KA carriers (commercial products from Süd-Chemie AG).
- KA carriers commercial products from Süd-Chemie AG.
- the filter cake is made by extruding, granulating or pelletizing into shaped bodies. The moldings will be then thermally treated as described below.
- the respective Starting substance with any inorganic and / or organic acid, preferably a mineral acid, such as Hydrochloric acid, sulfuric acid or phosphoric acid.
- the Acid activation can also occur at elevated and low temperatures or increased pressure. Here the specifics are generally increased Surface, which usually also increases the adsorption capacity brings with it. There is also an expansion of the lattice instead, resulting in an increase in pore volume and the average pore diameter.
- the Acid activation can also include additional chemical treatment, e.g. the surface is silanized.
- the moldings can be thermally charged with acid Undergo treatment.
- the thermal treatment includes drying, if necessary vacuum drying or spray drying and / or Calcination, preferably at temperatures of about - 200 to 600 ° C is carried out.
- the thermal treatment leads to a solidification of the expanded lattice structure and thus an increase in abrasion resistance.
- the thermal Treatment can be under oxidizing, reducing or inert conditions and in the presence of water vapor be performed. Thermal treatment can also be used acid activation.
- the pore volume of the shaped bodies is preferably approximately 0.1 to 2, in particular about 0.3 to 1 ml / g, the average pore radius about 0.2 to 6000 nm, in particular about 0.2 to 5500 nm.
- the injected volume of mercury based on the pore mass (ml / g) as ordinate depending on the pore radius as abscissa (in logarithmic Representation) gives the graphic representation of the Pore size distribution.
- the spaces between the particles are counted as pores if they are in a Pressure of 1 bar are filled with mercury. With this method only pores down to a radius of about 2 nm (Macro and mesopores) recorded.
- the zeolites are also through the channels of the zeolite lattice formed micropores with pore radii from about 0.2 to 2, preferably 0.25 to 0.7 nm (intracrystalline pore radii) effective.
- the radii of these pores are generally defined by Evaluation of the X-ray diffraction spectra determined.
- the meso- and macropores which are caused by the intergranular Spaces with pore radii from about 4 to 500, preferably about 5 to 300 nm, are effective. These are made using the method of mercury intrusion certainly.
- the non-zeolitic shaped bodies is adsorptive Neglect the effect of the micropores.
- These moldings preferably have an average pore radius of about 4 to 6000, in particular from about 5 to 5500 nm, which also after the method of mercury intrusion is determined.
- the degree of acid loading depends on the pore volume.
- the pores should preferably be 5% be loaded with acid up to 95%; preferably they are closed Load 20 to 80% with acid.
- Sulfuric acid is preferably used for the acid loading, since it only boils at 338 ° C. So there is no danger that the apparatuses corrode and the downstream ones Catalysts are inactivated. Is also well suited Phosphoric acid because it is even less corrosive than Sulfuric acid; however, the adsorption capacity is Phosphoric acid for basic nitrogen-hydrocarbon compounds slightly lower than that of sulfuric acid.
- the adsorbent can also with organic sulfonic acids or other organic acids with higher boiling points become.
- hydrochloric acid is not used for loading, since it is light evaporates and causes corrosion problems. You can also Hydrochloric acid vapors in the subsequent catalytic treatment the cleaned hydrocarbons (cracking, reforming) inactivate the precious metal catalysts.
- the process steps for the production of the shaped bodies can be modified in such a way that after the acid activation and shaping carried out a further acid activation becomes. Even after the thermal treatment, another Acid activation can be performed if there is a further increase of the pore radius is desired. At the loading of the thermal Treated moldings with acid can become another connect thermal treatment, but not as intensive is like the first thermal treatment because of evaporation the acid should be avoided if possible.
- the shaping is generally carried out by agglomeration, e.g. by granulating, extruding, pelleting or tableting.
- the average agglomerate diameter of the shaped bodies is generally> 0.5 mm.
- the moldings can be granules, spheres, extrudates, rings, cylinders, Spoked wheels, 'fancy shapes' or honeycomb bodies his.
- the finished moldings generally have an adsorption capacity from about 1 to 10% by weight (based on atomic nitrogen). This corresponds to those that are typically removed Nitrogen-hydrocarbon compounds, an adsorptive capacity from about 3 to 50% by weight. These connections generally have boiling points (at atmospheric pressure) of ⁇ 400 ° C.
- the processes for removing the nitrogen-hydrocarbon compounds from hydrocarbon mixtures are preferably carried out continuously, but can also be carried out batchwise, ie quasi-continuously.
- the composition and concentration of the adsorbed molecules, the pressure, the temperature and the space velocity are varied and adjusted in a suitable manner.
- the moldings used according to the invention are advantageously used to remove basic nitrogen-hydrocarbon compounds from refinery streams, preferably from C 2 to C 20 streams, in particular from C 3 to C 12 streams, for. B. from LPG, naphtha, gasoline, kerosene, diesel, heating oil and gas oils used.
- the product and educt streams can flow through the adsorbent bed recycled and with under adsorption conditions gaseous and / or liquid substances are diluted.
- Dilution media are usually paraffins, olefins, Naphthenes and / or aromatics, as well as hydrogen, inert gases and / or steam used.
- the moldings used according to the invention can be used be regenerated.
- the acid and the basic nitrogen-hydrocarbon compounds adsorbed therein can be removed by washing. Subsequently the acid-free moldings are dried and again with Load acid.
- the moldings can also by oxidation of the adsorbed basic nitrogen-hydrocarbon compounds be regenerated. If the oxidation at elevated Temperatures are carried out at which part of the Evaporated acid, the evaporated acid is impregnated the molding is supplemented with new acid.
- the calcined balls are then 1000 liters 20% hydrochloric acid added and leached at 90 ° C for 24 hours.
- the leached balls are then washed with distilled water washed free of chloride and dried at 200 ° C for 10 hours.
- the calcined Clay balls placed in a suitable container in which a 50% sulfuric acid solution. The balls become complete saturated, then the excess is left Drain off sulfuric acid; the acid-impregnated balls dried at 110 ° C for 5 hours. Because of the evaporated water the degree of pore filling is about 40%.
- the granules are then placed on a pelletizing plate brought. Then the granules with concentrated sulfuric acid sprayed. With a sulfuric acid absorption of 30% by weight the impregnation is ended. Pore filling degree: 73%.
- Diatomaceous earth is formed together with 100% phosphoric acid into extrusions with a diameter of 6 mm.
- the extrudates are heated at 400 ° C. for 10 minutes.
- the nominal composition of the adsorbent thus obtained is: SiO 2 30% by weight; H 3 PO 4 70% by weight.
- Pore volume of the loaded adsorbent 0.22 ml / g; average pore radius: 1300 nm.
- Nominal composition of the adsorbent SiO 2 35% by weight; H 3 PO 4 65% by weight.
- Example 3 The granules of acid-activated montmorillonite obtained according to Example 3 are loaded as in Example 3 with (a) 9 or (b) 35% by weight H 3 PO 4 . Pore filling degree: 16.5% (a), 90% (b).
- the balls of acid-activated montmorillonite obtained according to Example 1 are loaded with 30% by weight H 3 PO 4 as in Example 5. Pore filling degree: 33%.
- 2500 g of commercially available Y zeolite are placed in a 10 liter mixer kneader and 700 g boehmite (manufacturer CONDEA) dry mixed. After adding 200 g of acetic acid and 2500 g of deionized water creates an extrudable mass. The mixture is in one Extruder pressed into full cylinders with a diameter of 1.5 mm.
- the extrudates are cut to size with a cutter Cut length of 3 mm, dried at 100 ° C and then Calcined for 5 hours at 600 ° C.
- Pore volume (after mercury porosimetry): 0.40 ml / g. Average pore radius: 170 nm.
- Micropore volume of the zeolite portion (x-ray): 0.53 ml / ml; Pore radius: 0.35 nm.
- 1000 g of the extrudates obtained are immersed in 1300 ml of a sulfuric acid with a concentration of 1346 g H 2 SO 4 / liter for 30 minutes at room temperature.
- the extrudates are filtered through a suction filter and dried then at 100 ° C. Pore filling degree: 72%.
- Nominal composition of the adsorbent alpha-Al 2 O 3 70% by weight; H 2 SO 4 30% by weight.
- Nominal composition of the adsorbent TiO 2 65% by weight; H 2 SO 4 35% by weight.
- 140 g of silicon dioxide in the form of extrudates with a diameter of about 4.5 mm are in 350 ml of a sulfuric acid with a concentration of 745 g H 2 SO 4 / liter Immersed for 30 min at room temperature.
- the extrudate is filtered off through a suction filter and then dried at 100.degree.
- Nominal composition of the adsorbent SiO 2 70% by weight; H 2 SO 4 30% by weight. Pore filling degree: 33.5%.
- Nominal composition of the adsorbent ZrO 2 80% by weight; H 2 SO 4 20% by weight.
- the adsorbent of Example 2 is based on its absorption capacity regarding nitrogenous bases at different temperatures examined.
- the adsorbent of Example 2 is based on its absorption capacity regarding nitrogenous bases when using different Feed streams examined.
- Example 2 The absorbent of Example 2 is based on its absorption capacity for nitrogenous bases in the flow reactor different temperatures and different feed streams examined.
- the mixture is heated to the desired temperature in a stream of nitrogen (50 ° C or 100 ° C).
- the feed is over the adsorber bed pumped.
- gas chromatography is used analyzed for pyridine breakthrough and so the runtime or the absorption capacity until breakthrough is determined.
- the adsorbent of Example 2 is based on its absorption capacity regarding nitrogenous bases in the presence of thiophene examined in the flow reactor at different feed streams.
- the feed is over the adsorber bed pumped.
- the runtime is at the reactor outlet or the absorption capacity until breakthrough is determined.
- the thiophene conversion is 0%.
- the adsorbent of Example 2 is based on its absorption capacity regarding nitrogenous bases in the presence of thiophene in Flow reactor examined in a long-term test under pressure.
- the feed is over the adsorber bed pumped.
- gas chromatography is used analyzed for pyridine breakthrough.
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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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
- statisch - Raumtemperatur /24 Stunden
- Stammlösung: 2000 ppm Pyridin in n-Pentan
- 10 - 20 ml Stammlösung
- 40 - 50 mg Adsorbens als 1-2-mm-Granulat (die größeren Kugeln wurden zerkleinert).
Adsorbens Beispiel Nr. | MAXIMALE AUFNAHMEKAPAZITÄT | |
g Pyridin/100 g | g N/100 g | |
1 | 19,6 | 3,5 |
2 | 31,0 | 5,5 |
3 | 26,2 | 4,6 |
4 | 14,3 | 2,5 |
5 | 12,1 | 2,1 |
6 (a) | 6,4 | 1,1 |
6 (b) | 12,1 | 2,1 |
7 | 12,1 | 2,1 |
8 | 14,1 | 2,5 |
9 | 16,4 | 2,9 |
10 | 18,6 | 3,3 |
11 | 13,0 | 2,3 |
12 | 19,4 | 3,4 |
13 | 28,2 | 5,0 |
14 | 29,0 | 5,1 |
- statisch
- T = 25°C / 55°C / 90°C / 120°C / 135°C / 150°C
- 100 g Hexadecan
- 5 g Pyridin
- 15 g Adsorbens nach Beispiel 2 in Kugelform
Temperatur (°C) | UMSATZ PYRIDIN (%) | MAX. AUFNAHMEKAPAZITÄT (g N / 100 g) |
25 | 100 | 5,9 |
55 | 100 | 5,9 |
90 | 98 | 5,8 |
120 | 97,5 | 5,8 |
135 | 97 | 5,7 |
150 | 97 | 5,7 |
- statisch
- T = 100°C
- 15 g Adsorbens von Beispiel 2 in Kugelform
- Feed 1:
- 100 g Hexadecan
- 5 g Pyridin
- Feed 2:
- 100 g Hexadecan
- 5 g Pyridin
- 2 g Hexen-1
- Feed 3
- 100 g Hexadecan
- 5 g Pyridin
- 0,3 g H2O
- Feed 4
- 100 g Hexadecan
- 5 g Pyridin
- 0,5 g n-Butylmercaptan
Feed-Nr. | UMSATZ PYRIDIN (%) | MAX. AUFNAHMEKAPAZITÄT (g N/100g) |
1 | 100 | 5,9 |
2 | 99,7 | 5,9 |
3 | 100 | 5,9 |
4 | 100 | 5,9 |
- Feed : 250 ppm Pyridin in n-Heptan
- Temperatur: 50°C / 100°C
- Druck: atmosphärisch
- WHSV: 10 h-1
- Adsorbens: nach Beispiel 2, zerkleinert als 1-2 mm-Granulat
Temperatur (°C) | Laufzeit bis zum Durchbruch (h) | Aufnahmekapazität (g N / 100 g) |
50 | 82 | 3,8 |
100 | 68 | 3,2 |
- Feed : 250 ppm Pyridin in n-Heptan mit 1800 ppm Thiophen
- Temperatur: 50°C
- Druck: atmosphärisch
- WHSV: 10 h-1
- Adsorbens: aus Beispiel 2 als 1-2 mm-Granulat
Temperatur (°C) | Laufzeit bis zum Durchbruch (h) | Aufnahmekapazität (gN / 100 g) |
50 | 90 | 4,5 |
- Feed: 65 ppm Pyridin in n-Heptan mit 1800 ppm Thiophen
- Temperatur: 100°C
- Druck: 16 bar abs.
- WHSV: 5 h-1
- GHSV: 0,08 Nl H2/gxh
- Adsorbens: von Beispiel 2 als 4-5 mm Kugeln
Claims (15)
- Verwendung von porösen, anorganischen Formkörpern, deren Poren zu 2 bis 95% mit Schwefelsäure, Phosphorsäure oder festen Säuren beladen sind, zur Entfernung von basischen Stickstoff-Verbindungen, insbesondere Ammoniak oder basischen Stickstoff-Kohlenwasserstoff-Verbindungen, aus ammoniak- und/oder kohlenwasserstoffhaltigen Gemischen.
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die basischen Stickstoff-Kohlenwasserstoff-Verbindungen 1 bis 20, vorzugsweise 1 bis 12, Kohlenstoffatome enthalten.
- Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Formkörper aus porösen Substanzen, wie Kieselsäuren, Schichtsilicaten, Tonerden, Zeolithen, Titandioxid, Zirkondioxid und deren Gemischen gebildet sind, die mit flüssigen oder festen Säuren beladen sind.
- Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Formkörper und/oder deren Ausgangsmaterialien mit Säure aktiviert worden sind.
- Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß die Säureaktivierung mit Mineralsäure durchgeführt worden ist.
- Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Formkörper vor der Beladung mit Säure einer thermischen Behandlung bei Temperaturen von 200 bis 600°C unterzogen worden sind.
- Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Formkörper ein Porenvolumen von 0,1 bis 2, vorzugsweise von 0,3 bis 1 ml/g, und einen mittleren Porenradius von etwa 0,2 bis 6000 nm, vorzugsweise von 0,2 bis 5500 nm haben.
- Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß man Zeolith-Formkörper mit einem intrakristallinen Porenradius von 0,2 bis 2 nm, vorzugsweise von 0,25 bis 0,7 nm, und einem interkristallinen Porenradius von 4 bis 500, vorzugsweise von 5 bis 300 nm, verwendet.
- Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß man nicht-zeolithische Formkörper mit einem mittleren Porenradius von 4 bis 6000 nm, vorzugsweise von 4 bis 5500 nm, verwendet.
- Verwendung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Poren zu 20 bis 80%, mit Säure beladen sind.
- Verwendung nach einem der Ansprüche 1, 2 und 4 bis 9, dadurch gekennzeichnet, daß ein Zeolith verwendet wird, der überwiegend in der H+-Form vorliegt.
- Verwendung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß der mittlere Agglomeratdurchmesser der geformten Adsorbentien >0,5 mm ist.
- Verwendung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Formkörper ein Adsorptionsvermögen von 1 bis 10 Gew.-% (bezogen auf atomaren Stickstoff) haben.
- Verwendung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß der Adsorptionsprozeß unter folgenden kinetischen Parametern durchgeführt wird: Druck p = 0,5 bis 300 bar, vorzugsweise 1 bis 50 bar, Temperatur T = 0 bis 300°C; vorzugsweise 20 bis 150°C; Flüssigphasenadsorption: LHSV = 0,05 bis 50 h-1, vorzugsweise 0,5 bis 20 h-1; Gasphasenadsorption: GHSV = 10 bis 100.000 h-1, vorzugsweise 100 bis 10.000 h-1.
- Verwendung nach einem der Ansprüche 1 bis 14, zur Entfernung von basischen Stickstoff-Kohlenwasserstoffverbindungen aus Raffinerieströmen, vorzugsweise aus C2- bis C20-Strömen, insbesondere aus C3- bis C12-Strömen, vorzugsweise aus LPG, Naphtha, Benzin, Kerosin, Diesel, Heizöl und Gasölen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4429643A DE4429643A1 (de) | 1994-08-20 | 1994-08-20 | Säurebehandelte anorganische Formkörper und deren Verwendung |
DE4429643 | 1994-08-20 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0697454A2 EP0697454A2 (de) | 1996-02-21 |
EP0697454A3 EP0697454A3 (de) | 1996-04-24 |
EP0697454B1 true EP0697454B1 (de) | 2000-05-03 |
Family
ID=6526213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95112751A Expired - Lifetime EP0697454B1 (de) | 1994-08-20 | 1995-08-12 | Säurebehandelte anorganische Formkörper und deren Verwendung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0697454B1 (de) |
DE (2) | DE4429643A1 (de) |
ES (1) | ES2147249T3 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5770047A (en) * | 1994-05-23 | 1998-06-23 | Intevep, S.A. | Process for producing reformulated gasoline by reducing sulfur, nitrogen and olefin |
ES2153633T3 (es) * | 1996-03-28 | 2001-03-01 | Int Fuel Cells Corp | Extraccion de amoniaco de una corriente de combustible de una celula de combustible acida. |
DE19901049B4 (de) * | 1999-01-14 | 2011-03-10 | Ftu Gmbh Forschung Und Technische Entwicklung Im Umweltschutz | Mittel zur Reinigung von Gasen und Abgasen und ihre Verwendung |
DE10127927A1 (de) * | 2001-06-08 | 2002-12-12 | Sued Chemie Ag | Verfahren zur Herstellung von Adsorptionsmittelgranulaten auf der Basis von säureaktiven Schichtsilicaten und deren Verwendung zur Entfernung von Olefinen aus Aromaten oder Aromatengemischen |
DE102008059340A1 (de) * | 2008-11-30 | 2010-06-10 | Süd-Chemie AG | Katalysatorträger, Verfahren zu seiner Herstellung sowie dessen Verwendung |
Family Cites Families (13)
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GB1063201A (en) * | 1962-08-20 | 1967-03-30 | Union Carbide Corp | Improvements in and relating to three dimensional crystalline materials |
FR2438083A1 (fr) * | 1978-10-02 | 1980-04-30 | Mobil Oil Corp | Procede pour eliminer les composes azotes presents dans les hydrocarbures liquides |
US4419219A (en) * | 1981-09-24 | 1983-12-06 | Exxon Research And Engineering Co. | Adsorption of basic asphaltenes on solid acid catalysts |
DE3264921D1 (en) * | 1981-09-24 | 1985-08-29 | Exxon Research Engineering Co | Separating basic asphaltenes using metal oxide acid catalysts |
US4422926A (en) * | 1981-09-24 | 1983-12-27 | Exxon Research And Engineering Co. | Separating basic asphaltenes using Bronsted acid transition metal oxide acid catalysts |
CA1200221A (en) * | 1983-02-10 | 1986-02-04 | Marc-Andre Poirier | Removal of nitrogenous compounds from petroleum processing products using chlorosilylated silica gel |
CA1209927A (en) * | 1983-10-03 | 1986-08-19 | Majesty (Her) In Right Of Canada As Represented By The Minister Of Energ Y, Mines And Resources Canada | Removal of nitrogenous compounds from petroleum processing products using bromine-treated ilmenite |
EP0189606B1 (de) * | 1985-02-01 | 1989-08-09 | European Atomic Energy Community (Euratom) | Verfahren zur selektiven Adsorption von Schwefelverbindungen aus gasförmigen Gemischen, welche merkaptane enthalten |
US4846962A (en) * | 1987-02-12 | 1989-07-11 | Exxon Research And Engineering Company | Removal of basic nitrogen compounds from extracted oils by use of acidic polar adsorbents and the regeneration of said adsorbents |
US5013335A (en) * | 1987-06-30 | 1991-05-07 | Uop | Process for sequestering ammonia and the odor associated therewith |
DE4140455A1 (de) * | 1991-12-05 | 1993-06-09 | Zentralinstitut Fuer Physikalische Chemie, O-1199 Berlin, De | Abriebfeste und poroese komposit-formlinge und verfahren ihrer herstellung |
DE4305781A1 (de) * | 1992-05-22 | 1993-11-25 | Solvay Catalysts Gmbh | Sorption von NH¶3¶ mit dotierten oxidischen Sorbenzien |
DE4243389A1 (de) * | 1992-12-21 | 1994-06-23 | Sued Chemie Ag | Verfahren zur Herstellung von Sorptionsmitteln zur Aufnahme von Flüssigkeiten |
-
1994
- 1994-08-20 DE DE4429643A patent/DE4429643A1/de not_active Withdrawn
-
1995
- 1995-08-12 DE DE59508247T patent/DE59508247D1/de not_active Expired - Fee Related
- 1995-08-12 EP EP95112751A patent/EP0697454B1/de not_active Expired - Lifetime
- 1995-08-12 ES ES95112751T patent/ES2147249T3/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0697454A3 (de) | 1996-04-24 |
EP0697454A2 (de) | 1996-02-21 |
DE4429643A1 (de) | 1996-02-22 |
ES2147249T3 (es) | 2000-09-01 |
DE59508247D1 (de) | 2000-06-08 |
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