TWI312765B - Active charcoal with improved mechanical strength and its uses, in particular, as catalyst support - Google Patents

Description

13 12% & 1 〇 3217 Patent Application Chinese Manual Replacement Page (July 96) IX. Description of the Invention: [Technical Field] The present invention relates to a reaction catalyst carrier. Activated carbon which can be used especially in the liquid phase, especially for the oxidation of mercaptans present in liquid hydrocarbons. [Prior Art] The oxidation reaction of thiol present in liquid hydrocarbons Catalyst (usually deposited on porous solids

The action of the bismuth cobalt phthalocyanine on the battle body oxidizes the thiol present in the hydrocarbon to a disulfide: 2 RSH + 1/2 02 ~>RSSR + Η20 The reaction is in an inert medium (sodium hydroxide) A catalyst based on (tetra) cyanine is used for catalysis. For heavy petroleum feedstocks (Fluid Fluid Catalytic Cracking (FCC) gasoline, kerosene, diesel), in order to accelerate the reaction of heavier and thus less reactive rsH compounds than light RSH compounds, a solid support is utilized for the catalyst. Furthermore, the isothiol is therefore heavier and it is not extracted from the organic phase. In this case, the content of sulfur is constant; therefore, the term “de-sweet.” is used to convert to disulfide, which is lighter than mercaptan. The main application is the production of gaseous fuel.

Basu et al., Catal. Rev. Sci. Eng., 35(4), 571-609 (1993) The paper entitled "Merox and Related Metal Phthalocyanine Catalyzed Oxidation Processes" is a self-supporting, catalyst, blending A summary of the disclosure of the subject matter and its exhaustive aspects from the standpoint of hetero-additives, reaction mechanisms, and the like, among which numerous types of carriers are described: 99413-960724.doc 1312765 Clay, alumina, activated carbon, or any other Solid supports, but it has been found to be preferred to use carriers made of carbonaceous materials. The disclosure teaches that activated carbon is generally more effective than other supports from the viewpoint of catalytic catalytic kinetics: see Oxidation of ethyl mercaptan over cobalt phthalocyanines f Huendorf U. k, Heterog. Catal., 6(2), 73 (1987);

Phthalocyanines on mineral carriers, 4a), Low-molecular-weight and polymeric phthalocyanines on SiO2 and A12〇3 and active charcoal as catalysts for the oxidation of 2-mercaptoethanol, W0hrle D. et al., Makromol.

Chem., 190, 961-974, (1989). In US 4 24 8 694, UOP teaches that the use of high density carbon having an overall density between 0.25 and 0.5 g/cm3 results in better catalytic kinetics than low density activated carbon. In the example, UOP demonstrates a better candidate for a charcoal Darco MRX with a density of 0.44 g/cm3 than a charcoal Nuchar WA with an overall density of 0.15 g/cm3. In the current industrial practice of hydrocarbon desulfurization, only activated carbon is used as a catalyst support. The main methods for the desulfurization of petroleum raw materials or industrial hydrocarbons are known by the names of Merox (UOP technology), Mericat (Merichem technology) and Sulfrex (IFP technology): ♦ Merox technology developed by UOP (the principle is in US 3 371 Detailed description of 031) relates to the oldest and common method: it consists of a simple fixed bed operated by diafiltration from the top, followed by a hydrocarbon/sodium hydroxide separation drum, ♦ Merichem's newly developed Mericat technology. The system, the principle of which is set forth in EP 203 574, has a fiber precontactor followed by an activated carbon bed operated by a bottom up mold 99413.doc 1312765; the separator is integrated with the tower (which makes the unit more compact), ♦ IFP The principle of the developed Sulfrex technology is set forth in the patent ❿ 2 56 889 889. - In these various desulfurization processes, activated carbon is placed in a column and then wetted in water. It is then impregnated with a dilute solution of a catalyst substantially based on sulfonated cobalt phthalocyanine by diafiltration through a column (until reasoning, often carried out in situ in a scouring tower. However, it can also be in two = as in 'Merox Processes J.r. caustic minimization and management, Holbrook et al., (UOP), NpRA 1993 Annual Meeting, mid-year instructions. Subsequently, the activated carbon bed was completely treated with sodium hydroxide solution (sodium hydroxide concentration: 5 wt% to 20% by weight) impregnation. Finally, the reaction can be started by simultaneously diafiltration of the hydrocarbon feedstock to be treated and the recovered sodium hydroxide solution, and a minimum amount of air is added thereto for the reaction. The reaction is at medium temperature and medium pressure. ^ Operating at a force of about 0.1-1 MPa (ll 〇 bar) and preferably about 35-50 C and 0.4-0.6 MPa (4-6 bar). The contact time varies from a few minutes to a few hours. Preferably 30 to 60 minutes. The concentration of mercaptan at the inlet is several hundred ppm at the outlet of the unit to less than 3 〇 ppm. Industrial problems that may be encountered are rarely attributed to poor catalyst (meaning from RSh • Conversion of compounds to disulfide Insufficient) - In addition, in this case, re-impregnation of the carrier with a catalyst is sufficient to restore good efficacy - but due to the mechanical resistance of the activated carbon. This is because the latter is subjected to mechanical deer's, especially when fluid When the power condition exceeds the normal standard (high flow rate, high flow rate 99413.doc 1312765 and the like), the treatment process requires a layer of ceramic beads under the activated carbon bed, which causes the activated carbon to withstand additional mechanical stress, and the like. These conditions can destroy the particles of activated carbon and form fine powder. If it accumulates, it will produce a significant increase in the pressure drop (pressuredr〇p), which can be sustained until forced to stop the latter to remove the fine powder. Even actually changing the feed of activated carbon completely, even if the catalyst is still effective. Because the long-term shutdown of the refinery is wasteful, it is obviously necessary to (4) control the situation. Remove the fine powder and change the carbon feed. It is best to avoid unproductive operations. The operation of wetting and the operation of impregnating carbon with a catalyst are also ineffective. It may be faster to proceed. From this point of view, it is more advantageous to wet and impregnate the carbon system faster. Finally, in some cases, the treated petroleum raw material becomes colored, and the coloring is attributed to the occurrence A side reaction catalyzed by impurities such as iron oxide. Therefore, it is required that the body contains as few impurities as possible, especially metal impurities. [Invention] The present invention relates to an activated carbon which is used as a liquid phase reaction (especially a liquid state). The catalyst carrier of the oxidation reaction of a thiol present in a hydrocarbon does not exhibit the above disadvantages. The activated carbon according to the invention is characterized by: • greater than or equal to 1.00 ml/g, preferably greater than or equal to the total pore volume of U, A bed strength (Bs) greater than or equal to MPa (10 bar) and preferably greater than or equal to M5 Mpa (15 (four), and advantageously greater than or equal to 1.7 MPa (17 bar), based on the overall crush test amount of the Shell, And 99413.doc 1312765 • a bet specific surface area greater than or equal to 5〇〇m2/g′ preferably greater than or equal to 700 m2/g, and, preferably, • a micropore volume system greater than or by nitrogen adsorption measurement Equal to 〇 2 〇 ml/g, preferably greater than or equal to 30.30 ml/g. • The mesopore volume system is measured by nitrogen adsorption and mercury intrusion to be greater than or equal to 0.15 ml/g', preferably greater than or equal to 2 〇 ml/g.

• The macropore volume measured by mercury intrusion is greater than or equal to 〇 4〇 ml/g, preferably greater than or equal to 〇.50 m〗/g. In this paper, the definitions of micropore, mesopores, and macropore volumes are consistent with the mpAC standard. Advantageously, the activated carbon according to the invention has less than or equal to 2 〇〇〇 ppm by weight 'preferably less than or equal to 1000 ppm, advantageously less than or equal to 5 〇〇 ppm and more advantageously less than or equal to 3 The iron content of the melon (by weight). In the activated carbon according to the present invention, it is also preferred that they have an overall density of between 0.20 and 0.50, preferably between 0.3 and 〇4. Among the activated carbons according to the present invention, those having a ash content of less than or equal to 1% by weight, preferably less than or equal to 7% (measured according to the cefic method) are at 650. (: the total weight of the activated carbon before combustion. The particle size of the activated carbon according to the invention is generally such that the carbon particles consist of a mesh having 0.2 faces, preferably G.4 mm and advantageously G 6 _ The screen of the size is retained and passed through a screen having a width of 5 mm, preferably 2. The size of the mesh according to the invention can be provided in various forms, for example 994J3.doc 1312765 main two bundles, for example by powder form The initial carbon-containing source, the calendar-type sputum agent and the like are coagulated, and then activated, the granules, for example, are obtained by crushing the activated spur fragments and screening the desired granules. The particles or any other shape of the particles preferably have a particle size of the above-mentioned preferred activated carbon in the form of particles or beads. The activated carbon produced by the fully activated core is especially based on the slag slag. A preferred feature of the invention is that it is mechanically particularly (iv), rapidly impregnated with an oxidizing catalyst, and exhibits a low inorganic impurity content and is therefore particularly suitable for use as a carrier for an oxidation catalyst for a particularly long period of time. Based on the core and advantageously based The activated carbon of the slag can be manufactured according to conventional methods 'that is by physical activation or by chemical activation. It should be understood that the term "physical activation" means that the first stage is usually under the influence of The enthalpy is suspended at a steam activation stage of approximately 900 C; it is understood that the term "chemical activation" means that the carbonaceous feedstock is impregnated with a chemical such as phosphoric acid or zinc hydride, followed by typically at about 5 Torr. Activating, followed by a washing operation to recover the used chemical. The present invention also relates to a method of impregnating such activated carbon with an oxidation catalyst and using the supported catalyst for thiol oxidation in a liquid phase manner. Use: A metal complex as an oxidation catalyst is used to impregnate the activated carbon; in the metal complex, mention may be made of cobalt, nickel, copper, zinc and vanadium phthalocyanine, polyaminoalkyl polycarboxylic acid The compound (such as a complex of EDTA or a salt thereof which has been disclosed in, for example, FR 2 56〇889, 99413.doc -10- 1312765), or any other metal complex, phthalocyanine, is especially preferred. Phthalocyanine is usually in aqueous solution Not directly soluble, and for this reason it is preferred to use one of its water-soluble derivatives such as acid-reduced or acidified derivatives, and it is preferred that the acidified derivative is particularly advantageous in which the 'di-acidified derivative is also advantageous. Add - # or a variety of promoters or promoters disclosed in the literature, such as, for example, acetic acid or methanol (us 4 〇 8 7 3 78), urea (10) 4 (four) 6 chuan, carboxylic acid (US 4 107 078) 'chlorination Trimethylammonium Ethanide or Ammonium Hydroxide (US 4 i 2 i 997 and US 4 124 494), Polynuclear Aromatic Acids (10) 4 121 998), Quarterly Record (10) 4 157 312), Hydroxyl Alcoholamine (10) 4 i59 946), morphine (us4 us 245) or monoethanolamine (still 4 956 325). The impregnation can be carried out before or after the carbon is placed in the industrial unit in which the thiol is oxidized to the disulfide reaction. Subsequently, the activated carbon bed is tested with an inert solution, typically 0% by weight of a gas oxidized nanosolution. / 〇 to 20% by weight of sodium hydroxide), potassium hydroxide solution or ammonia-containing solution is completely impregnated as disclosed in US 4 502 949 or US 4 913 802. Finally, the oxidation reaction of the mercaptan can be started, for example, by simultaneously diafiltration of the hydrocarbon feedstock to be treated and the recovered alkaline solution (sodium hydroxide solution, potassium hydroxide solution, ammonia-containing solution, and the like). The reaction has been carried out to which a minimum amount of air has been added. The reaction is usually operated at moderate and medium pressures, i.e., about 20-8 (TC and 0.1-1 Mpa and preferably about 35_5 (rc and 〇·4-0·6 Mpa. The contact time is usually from a few minutes to a few The change between hours, preferably 30 to 60 minutes. The concentration of sulphur fermentation varies from about a few hundred at the inlet to less than 30 ppm at the outlet of the saponin. 99413.doc -11· 1312765 favored by Applicant The core-based activated carbon has very good impregnation kinetics and is therefore rapidly placed in place; its catalytic performance is equivalent to that of known carriers for industrial use; due to its excellent mechanical resistance, Therefore, the lifetime of the supported catalyst is increased compared to the lifetime of the carrier which has been used in the industry; in the end, the side reaction is very limited due to its very low iron content. The activated carbon according to the present invention can also be used for any of it. Catalyst support for type reaction, such as, for example, oxidation of cyanide present in water, as in Chemical oxidation: Technologies for the Nineties, Kurek PR (UOP), Proceedings First International Symposium, described in the heart, or as a catalyst for use in glyphosate synthesis, as disclosed in, for example, FR 2 269 533 and used for purification and/or separation by selective adsorption in liquid and/or gas phase The method (liquid food decolorization, water treatment, air treatment, solvent recovery, and the like). [Embodiment] Table 1 compares several activated carbons of different qualities and sources and lists their main features. It is determined according to standard methods, in detail CEFIC (c〇nseil Euroyen des FH & ati〇ns heart to (4) Shimique [European Chemical Industry Council]). Two industries are commonly used as hydrocarbon desulfurization. The commercial grade charcoal of the metal oxidation catalyst carrier, BGP MX sold by Ceca, and the Daixo MRX system sold by Norit are selected for reference. 99413.doc 12 1312765 Table 1 Measurement method Trade name BGPMX - NC35 GAC 10-30 Darco MRX source pine olive slag scorpion coal activation physical physics physical and physical bulk density (g/cm3) 0.20 0.39 0.51 0.50 0.40 CEFIC iodine price 680 850 1000 1000 510 CEFIC methylene blue Number 4 6 6 8 7 CEFIC Ash content (% by weight) 2.5 3.1 4.8 11.3 13.7 Iron content (ppmw) 70 200 150 4000 2000 Nitrogen adsorption BET specific surface area (m2/g) 760 870 1150 1050 560 Nitrogen adsorption + mercury intrusion method Pore volume (ml/g) 0.835 1.341 0.724 0.916 0.936 Nitrogen adsorption micropore volume <20 A (ml/g) 0.236 0.360 0.430 0.400 0.173 Nitrogen adsorption mesopore volume 20 A-70 A (ml/g) 0.06 0.05 0.02 0.12 0.11 Mercury intrusion volume 70 A-500 A (ml/g) 0.084 0.210 0.100 0.130 0.310 Mercury intrusion volume 500 Α-10 μπι (ml/g) 0.455 0.721 0.174 0.266 0.343

Special tests have been developed to demonstrate the performance of activated carbon as an oxidation catalyst support.

Example 1: Bed Strength Test This test measures the mechanical resistance of a bed of solid particles subjected to a uniformly distributed pressure. It draws inspiration from a Shell's overall crush test. The 20 cm3 adsorbent was placed in a metal cylinder with an inner diameter of 27.6 mm. The increased pressure in a stationary phase is applied to the top of the bed via a piston. The content of the fine powder (< 0.2 mm) formed between each stationary phase was determined by screening and weighing. The pressure necessary to obtain 0.5% by weight of the fine powder was then inferred therefrom by interpolation. Table 2 gives the results: 99413.doc -13- 1312765 Table 2. Activated bed strength Product name BGPMX - NC35 GAC 10-30 Darco MRX Source pine olive residue Coconut coal pressure (MPa) eg 0.5% fine powder 0.25 2.14 1.56 1.55 1.00 It is apparent that the olive residue-based activated carbon according to the present invention has the strongest mechanical resistance and is significantly higher than the carbon used in the two industrial applications in the present application. Example 2: Catalyst Impregnation Kinetics Test The use of Europhtal under the name 802 includes 30% acidification error

A catalyst solution of cyanine. 320 ml of activated carbon was introduced into 1 liter of water in a beaker. A small amount of the ammonia-containing solution is added so that the pH of the final solution after the addition of the ammonia-containing solution is greater than or equal to 9. A dose of Europhtal 802 catalyst was then introduced to give the final product a just 2 g dose of catalyst per liter of activated carbon. Slowly mix the mixture and sample it over time. The amount of catalyst still present in the solution is determined. This test can be performed by optically dense measurement at 660 nm after pre-correction of the device. The results are given in Figure 1 below. It can be seen that the slag-based activated carbon and Darco MRX according to the present invention are faster than others. They are the slowest based on wood and coconut, and their impregnation cannot be completed after 500 minutes. Example 3: Thiol Oxidation Catalytic Test Itb 湏!J Try to draw inspiration from the various types of ethyl mercaptan over cobalt phthalocyanines, Huendorf U et al., Heterog. Catal., 6(2), 73 " 99413.doc -14- 1312765 Pre-impregnated with 0.5 ml of activated carbon, 50 ml of sodium hydroxide solution (concentration: 7 wt%) and containing 2.81 g of untreated catalyst according to the test of Example 2 (ie 2 g catalyst / liter of charcoal) 140 g of n-heptane of butyl mercaptan was introduced successively into a 0.5 liter glass reactor maintained at ambient temperature with a jacket. The adjustment was started to 500 rpm, and a gas flow controlled at 1 liter/hour was introduced by bubbling into the solution. Samples of the organic phase were sampled over time to monitor the remaining thiol concentration. Thiol is determined by chromatography.

The initial RSH content is 20 000 ppm by weight. The results are given in Table 3 below. Table 3: Thiol oxidation kinetics trade name BGPMX - NC35 GAC 10-30 Darco MRX source pine olive residue slag coal 60 minutes after RSH content (ppm by weight) 4420 4950 8460 5010 4660 RSH content after 120 minutes (ppm Weight)) 1500 1700 7070 3200 1300 RSH content after 180 minutes (ppm by weight) 140 76 6130 1220 120 360 minutes after RSH content (ppm by weight) 32 33 4330 140 34 Three types of charcoal should be noted (BGP MX, Darco MRX and the olive residue-based activated carbon according to the invention exhibit more or less equal catalytic properties. In addition, the other two types of charcoal exhibiting significant mechanical resistance (GAC 10-30 and NC 35) have significantly lower catalytic kinetics compared to these. Obviously, only the activated carbon produced from the olive residue exhibits the best characteristics, namely, mechanically strong, fast impregnation, excellent catalytic performance, and exhibiting low inorganic impurity content (detailed iron). 99413.doc -15 -

13 12?6 & 10321.7 Patent Application Replacement Page (July 96) [Simplified Schematic] Charcoal and Darco Figure 1 shows that the MRS based on olive slag according to the present invention is faster than others.

99413-960724.doc 16-

Claims (1)

a·131 is 7 (65〇3217 application Chinese patent application scope replacement... Ten, patent application scope: 1. An activated carbon, characterized by: a total pore of 1.00 ml/g or more Volume, a bed strength (BS) greater than or equal to $ MPa (15 bar), and a BET specific surface area greater than or equal to 500 m2/g, based on the overall crush test from Shell. The activated carbon of the claim item is characterized by a total pore volume greater than or equal to i2〇m. The activated carbon of claim 1, which is characterized by greater than or equal to 7 chest (17 bar) bed strength (BS). The activated carbon of claim 1, which is characterized by a BET specific surface area greater than or equal to 鸠m2/g. 5. The activated carbon of claim 1, wherein the activated carbon is characterized by: a micro-strand greater than or equal to G.2() _ by nitrogen adsorption measurement 虱Adsorption and mercury intrusion method to obtain a volume of pores greater than or equal to 0·15 ml/g, and product: a large pore volume greater than or equal to 〇4〇_ is 0.30 ml/g by pressure measurement. 7. The pore volume of the activated carbon as claimed in claim 5. 8. Activated carbon as claimed in claim 5, wherein the activated carbon is characterized by being greater than or characterized by greater than or equal to 0.20 ml/g and characterized by greater than or equal to 0.50 ml/g. 99413-980417.doc 1312765 Large pore volume. 9. For example, in any of the items 1 to 8 of the eve, the present, and the mountain, the material of the charcoal, the money of which is less than or equal to 20 〇〇 ppm. The activated carbon of claim 9 is characterized in that its iron content is equal to or greater than 1000 ppm. η. The activated carbon of claim 9, which is characterized in that it is equal to 500 ppm. 12. The activated carbon of claim 9 characterized in or exclusively at 300 ppm. As claimed in any one of claims 1 to 8, it is characterized in that its overall density is between 0·20 and 0.50. 14. Activated carbon as in Item 13 is characterized by its entirety. The density is less than or equal to the iron content. The amount by weight is less than the iron content by weight. The amount of the iron is less than 15. The weight of the activated carbon according to any one of the claims (1) is characterized by the ash content. It is less than or equal to 1〇0/〇 based on the total weight of activated carbon. The activated carbon of claim 15 characterized in that the ash content is less than or equal to 7% based on the total weight of the activated carbon. The activated carbon according to any one of the preceding claims, characterized in that the particle size is such that the carbon particles are retained on a sieve having a mesh size of 〇·2 axes and passed through a sieve. A mesh having a mesh size of 5 mm and provided in the form of a strand. 18. The activated carbon of claim 17, wherein the particle size is such that the carbon particles remain on a screen having a mesh size of 0.4 claws. 19. The activated carbon of claim 17, wherein the particle size is such that the 99413-980417.doc 1312765 anaerobic particles are retained on a screen having a mesh size of 0.6 mm. An activated carbon according to the item of claim 7, wherein the particle size is such that the carbon particles pass through a sieve having a mesh size of 2 mm. 21. Activated carbon according to claim 17, characterized in that the particle size is such that the carbon particles are provided in the form of granules or beads. 22. As requested! Activated carbon according to any one of the preceding claims, characterized in that it is produced from a core. 23. The activated carbon of claim 22, which is characterized in that it is produced from 撖 撖. A method of impregnating an activated carbon according to any one of claims 1 to 23: a) using a metal complex selected from the group consisting of cobalt, nickel, copper, zinc and vanadium phthalocyanine and a polyaminoalkyl polycarboxylate An aqueous solution of the acid metal complex, and b) impregnated with an assay solution. 25. The method of claim 24 wherein the metal complex of the polyaminoalkyl polycarboxylic acid is an EDTA complex or a salt thereof. 2 6 'The method of claim 2, 4' which impregnates the activated carbon with an aqueous solution of ugly phthalocyanine. 27. The method of claim 24, wherein the activated carbon is impregnated with one or more promoter or dopant additives. 28. The method of claim 24 wherein the alkaline solution is sodium hydroxide, potassium oxyhydroxide or ammonia. 29. A catalyst for oxidizing a thiol to a disulfide, characterized in that it is attached to at least one metal complex or a polyaminoalkyl polycarboxylate metal complex as claimed in claims 1 to 23. Any of the activated carbon components. The catalyst for the oxidation of mercaptans of claim 29, which is characterized by being composed of cobalt, nickel, copper, zinc or phthalocyanine. 99413-980417.doc 1312765 3 1. The catalyst for thiol oxidation according to claim 29, which is characterized in that it consists of phthalocyanine. 32. The catalyst for thiol oxidation according to claim 29, characterized in that it is obtained according to the impregnation method of claim 24, it being understood that the impregnation stage b) can occur during the reaction of the thiol oxidation. 33. Use of activated carbon according to any one of claims 1 to 23 as a catalyst support. 34. For the use of item 33, it is used for cyanide oxidation or glyphosate synthesis in water. 35. Use of activated carbon according to any one of claims u23 as a catalyst. 36. The activated carbon of the item is used in a method of purification and/or separation by liquid phase, which is selectively adsorbed as in any one of claims 1 to 23 and/or in a gas phase manner. 37. The use of claim 36, which comprises liquid food decolorizing gas treatment or solvent recovery. Water treatment, empty 99413-980417.doc .1312^(^103217; Patent application. Medium: text 1 replacement (June 96) XI, schema: Member Uwi/33⁄4 300 400 in minutes of time Taiwan - BGPMX - olive slag - A - NO 35 - Η - GAC10-30 一太, Norit Darco MRX 99413-960724.doc