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    • 专利摘要:
    1467389 Claus catalyst RHONE PROGIL SA 27 Aug 1974 [30 Aug 1973] 37467/74 Heading B1E [Also in Division Cl] A catalyst for the Claus reaction has a specific surface area of at least 80 m<SP>2</SP>/g and comprises activated alumina and 1 to 20% wt (calculated as the oxides) of one or more compounds of yttrium or a lanthamide metal e.g. 'lanthanum, praseodymium, neodymium, samarium and gadolinium. The catalyst may also contain one or more compounds of Ti, Pb, Mo, Co, Ni, Fe and U. The catalyst may be formed by impregnation, coprecipitation or cogellation or by agglomerating a mixture of oxides or hydroxides of aluminium and oxides, hydroxides or other compounds of the lanthanide metals.
    公开号:SU826944A3
    申请号:SU742056162
    申请日:1974-08-29
    公开日:1981-04-30
    发明作者:Домас Жан-Клод；Дюпюи Жорж；Мишель Макс
    申请人:Рон-Прожиль (Фирма)；
    IPC主号:
    专利说明:

    (54) CATALYST FOR CLEANING GAS FROM CARBON AND HYDROGEN SULFUR COMPOUNDS
    This purification deficiency over time increases more and more and depends on the sulfation of catalysts, caused by the presence of traces of oxygen in the gases being treated and which is in this case progressive, but may occur due to the accidental penetration of air into the incompletely cooled catalysts when the plants are stopped.
    The result of this sulphation is a significant reduction in the activity of conventional catalysts with respect to the removal of carbonic sulfur compounds, as well as a decrease in the activity of the catalysts relative to the Claus reaction itself, especially if it is carried out at a relatively low temperature, as happens in the last converter where gas is fed. small content of N2 and maintain a temperature of about 200-220 C.
    A known catalyst for the purification of gases from carbon and hydrogen compounds of sulfur is an alumina with a specific surface area of from 80 to 300 m / g 2.
    The closest to the proposed technical essence and the achieved effect is a catalyst for gas purification, carbon and hydrogen sulfur compounds having a specific surface area of 80 to 300 m / g, containing titanium dioxide and aluminum oxide in the following ratio of components, weight. %: Tsvu titanium oxide 1-60, alumina the rest Z.
    The known catalyst is not sufficiently active. So, when cleaning gas containing, vol.%: 1; SOa.0,5; water 28; nitrogen The rest, when the sulfur yield is on a known catalyst containing 5 wt.%: T10d by 40%. The purpose of the invention is to increase the activity of the catalyst.
    This goal is achieved by the fact that the catalyst for the purification of gases from carbon and hydrogen compounds of sulfur, having a specific surface area of 80 to 300 m / g and containing alumina, contains oxide or metal oxides selected from groups. containing yttrium, lanthanum; and lanthanide with the following ratio of components, wt.%:
    Oxide or 01SISI
    metals 1-20 Alumina Else The proposed catalyst has an increased activity compared with the known catalyst and the sulfur yield during gas purification containing%: 1, 50.2.0.5, water 28, nitrogen remaining at 225 ° C is 48%.
    The catalysts can be manufactured in various ways, for example, by impregnating the carrier with active aluminum hydroxide with solutions of metal compounds that easily form
    corresponding oxides during thermal decomposition in air, and the concentration of the solution is chosen in such a way as to obtain the desired amount of catalytic elements
    in finished catalysts. Solutions most convenient for use are solutions of acetates, chlorides or nitrates of selected elements, additives of other metals, if their
    Presence is desirable, can be easily carried out, for example, by means of nitrates.
    Other suitable methods are the agglomeration of mixtures of oxides.
    with aluminum hydroxides, for example, active aluminum hydroxide and oxides, hydroxides or other compounds of various metals, and at least some of these
    various metal compounds may be in the form of gels, sols or solutions. It is also possible to co-precipitate various hydroxides or other compounds.
    or the formation of hydroxides gels or sol compounds, as well as the addition of sols by the introduction of some metals into other metals. Typically, the manufacturing process for these catalysts is completed by drying and activation.
    The proposed catalysts can be used in a fixed or moving bed, in flowing
    or in a volatile state, adapted in each case the dimensions of their grains.
    For the preparation of the proposed catatzator, an active
    aluminum oxide grade A 2/5 (balls 2-5 mm) and aluminum oxide mark SCS 250 4/6 (balls 4-6 mm).
    The main characteristics of these materials are given in table. one.
    Table 1
    These products are mainly formed by alumina. Impurity contaminants other than sodium contain c in amounts that can be neglected (Pe, etc.). Didyme chloride containing 75% neodymium chloride and 25% praseodymium chloride, chlorides of other elements, cerium or yttrium, or purified, with a titer of about 100%, or various salts, mineral or organic, are used for impregnation elements of TTT In the periodic table, the atomic number of which goes from 57 to 71 (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,). The catalyst was prepared as follows. Take, for example, 100 g of a carrier pre-activated by blowing it with a dry gas — air or nitrogen for 2 hours in order to remove all moisture possibly adsorbed by alumina. In this case, the pore volume of this carrier is 0.50 cm. / g. The impregnation of HocHTejui is carried out by introducing in 100 g of a carrier a water solution of the desired element IL1 of the mixture of elements. This impregnation is carried out, for example, by wetting or immersing in a bath, fixed or agitated with or without circulation of the impregnating solution, or by spraying this solution onto the carrier beads in a thin stirred layer (drum or tray). The carrier and the impregnating solution initially have an ambient temperature, but due to the heating from the soaking, the temperature can vary from about 20 to about. The duration of the impregnation may be from several minutes to several hours, depending on the method used. Due to the poor viscosity of the solutions used and the sufficient proportion of macropores in these carriers, which preclude any possibility of air inclusion, the impregnation of the catalysts is fairly uniform. Thus, the impregnated catalyst is allowed to drain to remove excess solution on the surface of the balls, which are then dried at a temperature of about 110 ° C by blowing hot air for 4 hours. Example 1. Soak dry in a tray, i.e. without excess solution relative to the volume. 1 kg of the SCS 250 4/6 carrier preactivated as indicated above 500 mm cm of acetic acid solution containing 28 g of lanthanum obtained by dissolving lanthanum carbonate in an excess amount of acetic acid (approximately 25%) with 500С. Spraying with a jet of compressed air is done manually. It is stopped every time when a portion of the balls on the surface become too wet. In such a case, several tens of seconds, or perhaps several minutes, are expected in order to dissolve the excess solution. Thus, the impregnation with the entire amount of the solution is carried out in this way for about 15 VMH and during this treatment the temperature of the alumina balls does not exceed 65 C. The analyzed composition of the catalyst obtained is as follows:% Loss 4.3 BON-92.5 LagO , 3.0, 15 Various impurities contamination 0.05 impurities (not analyzed) Example 2. Prepare three canalizers A, B and C by impregnating balls of active aluminum hydroxide (diameters from 2 to 4 mm, specific surface area 320 pore volume 0.50) aqueous solution containing the desired amount of chlorides once ary group A elements 111, so that after drying at 110 C and baking at 500 ° C for 4 hours, the catalysts contain quantities of these various elements, oxides of the distance m, equal to 3 wt.%. Three other catalysts D, E and F are made by progresses of the same beads with solutions of acetates of various elements 111 A of the group and are subject to the same heat treatment as catalysts A, B and C. The amount of their content in compounds calculated by oxides m is equal to but 7 wt.%;
    2.25 - .1.5
    0.9
    -, 0.6 0.15 0.15 0.15 0.15 Na, iO Various 0.05 0.05 0.05 0.05 impurities
    The non-impregnated active aluminum hydroxide is itself an effective catalyst and is tested here for comparison (Catalyst T).
    All of these catalysts are divided into two groups. The catalysts of the first group are kept as they are (initial state), the catalysts of the second group are sulfated
    5.25 7.0 - 11.25 1.75 - - 3.75
    heating to 4 hours in a mixture containing 70% air and 30% SOj. and used in this example to process a gas mixture containing,%: 2 3; SO 1.5; 23; , 5 in a reactor with a diameter of 22 mm. The contact time is 1 s, and the outlet temperature is 225 or 250 ° C. The gas analysis is carried out by chromatography. Reaction outlet Use: for catalyst A, a solution of didymium chloride containing 19.3 g of neodymium and 6.2 g of praseodymium, for a catalyst of B and a solution of hydrochloric acid containing 12.7 g of yttrium, 8j ;; 2 g of gadolinium and 5.4 g samari, for catalyst C, a hydrochloric acid solution containing 24.4 g of cerium, for catalyst D, a solution of acetic acid containing 45.9 g of neodymium and 14.4 g of preyodymium; for catalyst E, a solution of acetic acid containing 60.0 g of neodymium, for catalyst F, acetic acid solution containing 65.3 g of lanthanum, for catalyst H hydrochloric acid solution containing 98.3 g of neodymium and 30.8 g of praseodymium. Carbon loss for all catalysts is 3%. The compositions of the resulting catalysts are given in table. 2, Table 2 2 7.0 0.15 0.15 0.15 0.05 0.05 0.05 Claus p S0, j, two orders of magnitude greater than the ratio of the calculated HjS conversion to the maximum theoretical conversion,
    75% Nd-jOo, 3
    25% Pr, -0. 6 -fH
    50% YjO,
    30% GdjO 3
    From tab. Figure 3 shows the advantage of catalysts from A to F over catalyst T and the catalytic activity, somewhat superior to the catalytic activity of neodymium-based compounds, is revealed.
    Example 3. Two catalysts K and L are made by impregnating the same balls of active aluminum hydroxide as the balls used in example 1 with solutions of neodymium chlorides and praseodymium in the required concentrations in this way.
    K L
    40
    56
    280
    84
    80
    70
    70
    To obtain the number of compounds calculated from oxides m, equal to 7 and 15% of the finished catalysts, the neodymium / praseodymium ratio is the same as the ratio indicated in Table 2. 3 examples 2 for ka-, talizator A and D.

    These catalysts are sulfated, as in Example 1, and compared with catalysts A and T under the conditions of this example. The results obtained are shown in Table 4.
    iT a l and c a 4
    46 80 92 93
    280
    权利要求:
    Claims (3)
    [1]
    56 84 85 86 270 260 245 82694А10 obtained on the basis of thermodynamic calculation. The test results are given in the table. 3. Table 3 From table. 4, it can be seen that the catalytic activity of the catalysts increases more slowly when the content of compounds in them, calculated as oxides, exceeds 10 wt.%. Example 4. More accurately manufactured catalysts, iT and O are compared in the initial and sulphated state under the following conditions, almost the same as those in the second converter. The reactor used is similar to the reactor in Example 3. The gas mixtures to be treated contain,%: H, j, S 3; SO2. 1.5; H, 0 28 and, 5, and the temperature at the inlet and outlet of gases is 225 and, respectively. The outputs are determined as in Example 2 during the contact time 2 and 4 s. The test results are summarized in Table 5. Reaction Outputs Tables Claus Catalyst pSO ,,%, T-new100 T-sulphate 57 O-new100 O-sulphated 97 Example 5. This example refers to the same catalysts T and 0 tested under conditions the catalytic stages that correspond almost completely to the condition of the converter. The reactor is similar to the reaction in example 3, and iodine gas containing, in%, H-S 1; SO ,. 0.5 HjO 28 and, 5. The temperature at the inlet and at the outlet of the catalytic layer is respectively 210 and 22. The test results are shown in Table. 6. Table 6 Catalyst Claus pS02 reaction yields,%, for T-baseline .98 T-sulfated32 D-baseline97 0-sulfated77 From these results it can be seen that under the harsh conditions of the third covertor, it is possible to obtain much more sulfate in the catalyst. higher yield than with a reference catalyst consisting of active aluminum hydroxide. Example 6. Catalysts M, N and O are made by impregnating balls of active aluminum hydroxide with different specific surfaces and t grain diameters from 2 to 4 mm with the same solution of neodymium acetates and praseodymium, with such concentration that the catalysts contain after drying and calcining 7% by weight of the corresponding oxides, neodymium / praseodymium ratio as indicated in the previous examples. The resulting catalysts are treated at 450 ° C with a mixture of air and SOi and compared with catalyst D under the conditions of the experiment of Example 4. The results of the tests are shown in Table. 7.. Table 7 From the table, one can see the need for a sufficient specific surface area for these catalysts of at least 80 m / g. These examples do not limit the invention to the treatment of gases containing these compounds, it goes without saying that the inventive catalysts can be used to treat gas mixtures with a much higher content of sulfur compounds and, in addition, containing, for example, carbon dioxide and ammonia, which do not return to the reaction. . An example. An extruded catalyst of 20% 20% is prepared. Mixed and then continuously mixed at 60 ° C for 1,800 g of powdered activated alumina (granulometry 10-150 mm) and 200 g of lanthanum oxide, previously dried at 120 and crushed (15-40 mm), commercial product coming from Rochelle , with the gradual addition of 520 g of water to the mixer. The temperature of the mixture is maintained close to AZ. The paste thus obtained is then extruded in an Alexander-Berker-type extruder (an extruder product with a diameter of 1.8 mm). The resulting extrusion products are dried for 16 hours, then activated at 500 with hot air blowing for 4 hours. 414 Their composition is as follows,%: Loss on waste of 3.4, 6 La Oa19.9, 1 A catalyst with 1% of rare-earth oxides (75% NdeO- + + 25% Pr Oi) prepared by the methods indicated above corresponds to the final composition, %: Loss on waste 4,3AUOx94, 7 75% Nd, 0 ,, + 25% Pr, 0., 2. 4. P and The Claims of the Invention A catalyst for the purification of gases from carbon and hydrogen compounds of sulfur, including alumina and having a specific surface area of 80 to 300 m / g, is also distinguished by the fact that, in order to increase the activity of the catalyst, it additionally contains oxide or metal oxides selected from the group containing yttrium, lanthanum and lanthanide in the following ratio of components, wt.%: Oxide or metal oxides 1-20 Alumina Remaining Sources of information taken into account during the examination. Dupuy-Graulier Soufre -precede Catalytlque Claus, Inform iim, 1969, No. 74, p. 33-37.
    [2]
    2. The patent of France No. 1570161, cl. At 01 J, pub. 1969.
    [3]
    3.Patent of the USSR in application number 2014853 / 23-04, cl. &amp; 01 J 21/00, 08,04.74 (prototype).
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    同族专利:
    公开号 | 公开日
    BE819299A|1975-02-28|
    SE7410947L|1975-03-03|
    AT345254B|1978-09-11|
    CA1026309A|1978-02-14|
    IL45571D0|1974-11-29|
    FR2242144B1|1977-08-19|
    RO66351A|1979-06-15|
    ATA693674A|1978-01-15|
    DE2441199B2|1977-09-22|
    SE7703551L|1977-03-28|
    NO141594C|1980-04-23|
    US3978004A|1976-08-31|
    GB1467389A|1977-03-16|
    IL45571A|1977-06-30|
    DK456374A|1975-04-28|
    SE419536B|1981-08-10|
    DE2441199A1|1975-03-27|
    FI251074A|1975-03-01|
    DE2441199C3|1978-05-18|
    SE402270B|1978-06-26|
    FI58596B|1980-11-28|
    JPS521919B2|1977-01-18|
    ES429606A1|1976-10-01|
    JPS5051486A|1975-05-08|
    FR2242144A1|1975-03-28|
    NO141594B|1980-01-02|
    FI58596C|1981-03-10|
    NL7411437A|1975-03-04|
    IT1019142B|1977-11-10|
    NO743075L|1975-03-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2361825A|1941-08-25|1944-10-31|Union Oil Co|Reduction of sulphur dioxide to hydrogen sulphide and free sulphur|
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    US2972522A|1956-08-30|1961-02-21|Universal Oil Prod Co|Sulfur production|
    US3226340A|1960-05-04|1965-12-28|Ethyl Corp|Catalyst compositions comprising alumina with an inner lamina of metal oxide and an outermost lamina of copper oxide|
    US3322491A|1963-07-31|1967-05-30|Grace W R & Co|Method of treating exhaust gases|
    US3404100A|1963-10-21|1968-10-01|Exxon Research Engineering Co|Methane production using a promoted catalyst|
    US3346340A|1966-08-11|1967-10-10|Universal Oil Prod Co|Production of bromine by oxidation of hydrogen bromide|
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    CA1080441A|1975-12-24|1980-07-01|Gte Laboratories Incorporated|Catalytic process for removing sulfur dioxide from gas streams|
    DE2617649C2|1976-04-22|1983-03-03|Metallgesellschaft Ag, 6000 Frankfurt|Process for removing hydrogen sulfide and sulfur dioxide from exhaust gases|
    US4374819A|1979-11-13|1983-02-22|Gte Laboratories Incorporated|Catalytic process for removing toxic gases from gas streams|
    US4568664A|1980-07-21|1986-02-04|Aluminum Company Of America|Activated alumina Claus catalyst having increased sodium oxide content|
    US4364858A|1980-07-21|1982-12-21|Aluminum Company Of America|Method of producing an activated alumina Claus catalyst|
    US4608363A|1980-07-21|1986-08-26|Aluminum Company Of America|Activated alumina Claus catalyst having increased sodium oxide content|
    US4844720A|1982-04-02|1989-07-04|Amoco Corporation|Process for removal of hydrogen sulfide and hydrogen polysulfide from liquid sulfur|
    WO1984000702A1|1982-08-19|1984-03-01|Univ Southern Australia|Catalysts|
    FR2540092B1|1983-01-31|1986-02-21|Elf Aquitaine|CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM A H2S-CONTAINING GAS|
    FR2540006B1|1983-01-31|1988-04-01|Rhone Poulenc Spec Chim|HYDROGEN SULPHIDE OXIDATION CATALYST|
    US5171551A|1986-04-30|1992-12-15|Rhone-Poulenc Chimie|Zirconium dioxide gas desulfurization catalyst|
    FR2608458B1|1986-12-23|1989-03-10|Rhone Poulenc Chimie|CATALYST BASED ON CERIUM OXIDE AND METHOD FOR THE TREATMENT OF INDUSTRIAL GASES CONTAINING SULFUR COMPOUNDS|
    FR2625113B1|1987-12-23|1993-10-22|Rhone Poulenc Chimie|CATALYSTS FOR TREATMENT OF GASEOUS EFFLUENTS AND METHOD FOR TREATING SUCH EFFLUENTS|
    US5766567A|1990-02-13|1998-06-16|Elf Aquitaine Production|Method for desulphurising a gaseous mixture containing H2 S and SO.sub.|
    US5134107A|1991-09-06|1992-07-28|Ford Motor Company|Single phase metal-alumina made by sol-gel processing|
    US5260248A|1992-08-28|1993-11-09|Carus Corporation|Stable high temperature manganese based oxidation catalyst|
    US5512260A|1994-03-04|1996-04-30|Mobil Oil Corporation|Reduction of sulfur content in a gaseous stream|
    FR2734809B1|1995-05-30|1997-07-18|Elf Aquitaine|CATALYTIC DESULFURATION PROCESS OF A GAS CONTAINING THE H2S AND SO2 COMPOUNDS AND POSSIBLY COS AND / OR CS2, WITH RECOVERY OF THE SAID COMPOUNDS IN THE FORM OF SULFUR AND A CATALYST FOR THE IMPLEMENTATION OF THE SAID PROCESS|
    US6967063B2|2001-05-18|2005-11-22|The University Of Chicago|Autothermal hydrodesulfurizing reforming method and catalyst|
    FR2840295B1|2002-06-03|2005-02-04|Inst Francais Du Petrole|PRODUCT FOR REMOVING SULFUR FROM A LOAD CONTAINING HYDROGEN SULFIDE AND BENZENE, TOLUENE AND / OR XYLENES|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7331383A|FR2242144B1|1973-08-30|1973-08-30|
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