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    • 专利摘要:
    1437143 Treating exhaust gases; alumina RHONE-PROGIL SA 5 April 1974 [9 April 1973] 15152/74 Heading C1A [Also in Division B1] Waste gases containing hydrogen sulphide, sulphur dioxide and carbon derivatives of sulphur as impurities are treated for conversion of the impurities to sulphur, water and carbon dioxide in the presence of a catalyst comprising active alumina and 1 to 60% wt. of a titanium compound. calculated as titania, the catalyst having a specific surface area of at least 80 m.<SP>2</SP>/g. and optionally containing a compound of Mo, Co, Ni, Fe or U. In the examples temperatures of 260-335‹ C. and contact times of 1 to 8 seconds are used in the treatment of a gas mixture containing H 2 S, SO 2 , CS 2 , H 2 O and N 2 . The catalytic base is made by impregnating Al 2 O 3 pellets with TiCl 4 and calcining or agglomerating Al 2 O 3 with TiO 2 gel or sol.
    公开号:SU784739A3
    申请号:SU742014858
    申请日:1974-04-08
    公开日:1980-11-30
    发明作者:Дюпюи Жорж；Дома Жан-Клод；Мишель Макс
    申请人:Рон-Прожиль (Фирма)；
    IPC主号:
    专利说明:

    (5t) CATALYST FOR GAS CLEANING FROM HYDROGEN AND CARBON SULFUR COMPOUNDS The invention relates to catalysts for the purification of gases from hydrogen and carbon sulfur compounds. In the chemical industry, gaseous mixtures of complex compounds containing sulfur compounds are encountered, such as gaseous mixtures formed from the purification of natural and liquid hydrocarbons, and by cleaning these gaseous mixtures, sulfur can be recovered to contain sulfur compounds in already purified gaseous mixtures and finished for release to the atmosphere, reduced to a low degree, taking into account the introduction of increasingly stringent pollution standards. Typically, most of the sulfur of the gaseous mixtures treated is in the form of hydrogen sulfide and sulfur is recovered using the well-known Claus reaction carried out in a gaseous or liquid medium between the sulfur dioxide formed during the oxidation of the hydrogen sulfide and the residual hydrogen sulfide i. The Claus reaction, which is a reversible reaction, is carried out at the lowest possible temperature in order to contribute to the production of sulfur and can be carried out at a secondary temperature, provided it is activated by catalysts. However, the presence of other gaseous sedinium; Sulfur, such as carbon disulfide and carbon disulfide, significantly alters the drying method of gas purification based on the Claus reaction, therefore, the most active catalysts in the reaction do not have the same activity as the most active catalysts in the destruction carbon compounds of sulfur, which is carried out by hydrolysis, noTot iy that the optimum temperatures for these various reactions are not the same and because the presence of sulfur dioxide inhibits the hydrolysis reaction of carbon derivatives of sulfur. As a result, despite the fact that in industrial practice, baking / hdenes, in order to achieve better purification, process residual mixtures containing these different sulfur compounds, successively different catalysts, at the outlet of. The latter stage contains hydrogen sulfide and carbon compounds of sulfur in gases, which are usually tolerated by HopiviB. This lack of purification increases with time and possibly depends on the sulphurisation of catalysts occurring in the presence of; Traces of oxygen in the treated gases are progressive, but can also occur from the accidental penetration of air into incompletely cooled catalysts during the shutdown of the installations.
    The recommended catalysts for carrying out various reactions concerning gaseous sulfur compounds are numerous, most suitable and give interesting results if you do not try to get the most high plant capacity possible and if they allow relatively short duration of use without replacing with new catalysts. So bauxite, activated carbon, alkaline carriers, active aluminum hydroxide and catalysts consisting of sulphides, oxides or various compounds, of which molybdenum, titanium, cobalt, iron and uranium are located on carriers 2, were recommended.
    A well-known solution of a similar problem to the technical essence and the achieved effect is a catalyst for the purification of gases from hydrogen and carbon compounds of sulfur according to the Claus reaction, containing active alumina 3.
    The known catalyst is a 100% act of Alumina with a specific surface area of from 80 to 300. The catalyst is prepared by dehydrating hydrargillite in a stream of hot gases with a temperature of approximately 500-1,100 ° C, agglomerating the resulting active alumina in a dragee rotating boiler, ripening the agglomerates in a humid atmosphere at 30 ° C, then drying and calcining at a temperature of approx. allows you to clean, for example gas composition, about. 6; COS or CSti 1 SO 4, 2 Nf, - the rest, from sulfuric hydrogen compounds at 335 ° С by 80 - 88%.
    A disadvantage of the known catalyst is low activity.
    In order to increase the catalyst activity, a catalyst has been proposed for purifying gases from hydrogen and carbon sulfur compounds according to the Claus reaction, containing active alumina and additionally titanium dioxide in the following ratio of components, wt.%: Titanium dioxide 160, alumina else, and having a specific surface from 80 to 300 MVr.
    Distinctive features of the proposed catalyst are the additional content of titanium dioxide and cooTHOttieHHe components.
    The catalyst according to the invention has proven activity compared with the known. Thus, it allows to purify the gas of the above mentioned amount even under those conditions, as in the case of using a known catalyst of 100%.
    Catalysts in accordance with isoretenie can be obtained in different ways. For example, by impregnating active aluminum hydroxide with (Desired specific surface area with solutions of metal compounds that can easily decompose to the corresponding oxides when heated, and the concentration of the solutions is chosen in such a way as to obtain the desired amount of catalytically active components in the finished catalysts. Solutions most suitable for application titanium are solutions of titanium chlorides, oxychlorides or sulphates; however, other compounds can be used, for example, various organically salts, such as oxalates. Other metals, if their presence in the catalyst is desired, can be introduced, for example, in the form of nitrates.
    Other suitable methods include agglomerating mixtures of oxides or aluminum hydroxides, such as active aluminum hydroxide, and oxides, hydroxides, or other compounds of various metals, some of which may be in the form of gels, sols, or raatzors. It is possible to jointly precipitate various hydroxides or other compounds, or form CO-gels, hydroxides or CO-sols, as well as add sols that introduce some metals into compounds of other metals.
    In general, the manufacture of these catalysts is completed by drying and activation.
    The various catalysts of the invention may be used in stationary or moving layers, in a flowable or volatile state, in each case adapted to the size of their grains.
    The following are the various hymere results obtained in a fixed bed with catalysts consisting of aluminum and titanium hydroxides in proportions and obtained in various ways and methods. The first of these examples refers to an insufficiently strong catalyst without aluminum hydroxide and, therefore, not included in the scope of the invention, which consists only of THTaffa oxide with the desired specific surface area. This example is given in order to better show the abrupt titanium activity for the conversion of carbon derivatives of sulfur. Other examples allow us to determine the oscillation limits of the main parameters. In all of these examples, the gases are treated with various catalysts in a small reactor with a diameter of 60 mm. These gases have volumetric compositions,%: The contact time varies to 8 seconds and the outlet temperature varies from 2GO to. The gases leaving the reactor are analyzed by chromatography in order to determine the degree of conversion of 50.3 relative to the thermodynamically calculated output, as well as the degree of hydrolysis of CS, (carbon disulfide of the genus). Example. By heating the pH to 80 ° C and adjusting the pH to 1.1 by means of hydrochloric acid, the suspension is prepared from an aqueous suspension of titanium hydroxide containing 400 g of TU per 1 liter, obtained by precipitating ammonium hydroxide from a sulfur solution of sol, micelles equal to approximately 400 And in diameter. This sol is introduced drop by drop to the top of the glass reactor, content-. oil in its upper part (mixed with chlorofluorinated hydrocarbons and in its lower part. mixture in a 1/1 volume ratio of concentrated aqueous ammonia solution and suspended aqueous ammonium carbonate solution. The temperature of the reactor is maintained at. Thus, a dropping of stones occurs, then in the lower part the reactor collects balls with a diameter of 2 to 5 mm, which are then dried with air at. The balls thus obtained with a specific surface of 220 are divided into two parts. The first one is used as it is is, and the second is artificially sulphated by heating to a mixture of 70% air and 30% S0i2 for 4 hours.These two parts are used to treat the gaseous mixture of the above compounds.In addition, 3 as a comparison, gases are treated identically on alumina with the same dimensions and the same specific surface, either; in pure or sulphated form, the latter being achieved by the method used for titanium oxide balls. The following table. Figure 1 summarizes the results obtained and also shows the resistance values for the destruction of various catalysts. Table
    Sulphate Balls After Sulphation Sulphate Balls 3 100 100 100 After Sulphate 3 98 90 100 No 94, 90 45 9 83 15 97 98 78 97 80 35 00 100 100 00 00 00 From these results, it is clear that titanium oxide is superior to aluminum hydroxide in that as regards activity, as well as for the transformation of both SO and CS, j, and in particular, after sulphation. However, the resistance to destruction of titanium oxide balls is insufficient for industrial use. EXAMPLE 2 Concerning the results obtained with catalysts of various contents of titanium oxide obtained by impregnating active aluminum hydroxide balls with a specific surface of 300 and with a diameter of
    These results show the advantage of the content in the catalyst of titanium, which, in a proportion of 1% calculated by oxide, provides the destruction of the largest part of carbon sulphide. The strength of these various catalysts is sufficient and derives from the use of alumina hydroxide beads as a carrier.
    Example 3: Catalysts prepared by agglomerating alumina hydroxide powder and titanium hydroxide gel, which is a suspension of hydrolyzed titanyl sulfate, with a content of about 7% by weight 50 relative to Tg 0. Titanium hydroxide gel is mixed.
    190
    12
    195
    Dried and crushed to 79% by weight TiOij with active aluminum hydroxide powder with a particle size below 20 microns, obtained by partially dehydrating hydrargillite in a hot air stream in such proportions that the finished catalysts contain 10, 20, 40 and 60 wt. / g of Ti02 oxide. The mixture is moistened and agglomerated with 30 rotating granulator in the form of balls with a diameter between 2 and 5 mm. These balls mature for 24 hours at a temperature close to 100 seconds, then they are burned for 2 hours at 450 ° C in order to be activated. These catalysts are sulphated according to the method indicated in the preceding examples. The results are given in table. 3
    Table3
    20 45 97 35 65 100
    J
    30 57 98 4 G.
    100 between 2 and 4 mm solutions of titanium chloride in such a way as to obtain the desired oxide levels after drying the calcination at a temperature of 4 hours. These catalysts are sulphated before use according to the method described in the preceding example. All experiments were carried out at a temperature. The following table summarizes the results obtained for SO for a contact time of 5 s and for 05.2 for a contact time of 5 and 8 s, as well as the values of the specific surfaces of the catalysts and their resistance to fracture. The results are given in table. 2. Table2
    40% T 102.4+ hydroxide
    195 aluminum
    60% TiO f + hydroxide
    190 aluminum
    From tab. 3 shows the advantage of catalysts containing titanium, compared with the results obtained
    for luminescence hydroxide only. AT
    This type of catalysts obtained by agglomerating a mixture of oxides, it is necessary to use more titanium oxide in order to get very good results. However, this manufacturing method avoids the impregnation of titanium chloride, which has several disadvantages caused by the processing difficulties of this product.
    10% NO. + hydroxide
    200 aluminum
    20% TiO + hydroxide
    195
    LUMINUM
    30% Ti02 + H-hydroxide
    194
    CRYSTAL
    198
    191
    The results obtained in this example are similar to the results obtained in example 3.
    Example 5: The effect of the specific surface area of the catalysts on the results obtained is shown.
    Continued t & bl, 3
    82 100
    65
    100
    87
    100
    86
    66
    95,100
    Example4. This example relates to catalysts agglomerated in the form of balls with a diameter of 20-2 to 5 mm, obtained from aluminum hydroxide, identical to the aluminum hydroxide used in the previous example, and from sols of titanium hydroxide in such proportions as to obtain%: 10, 20, 30, 40 and 60 TiO contents in ready-to-use catheters. Sulfated catalysts are tested by the previously described method. The results are collected in the following table. four.
    thirty
    Table.
    70 100
    40
    96
    54
    25
    76,100
    49
    98
    65
    35
    81,100
    100 58
    85
    45
    100
    86
    100 69
    94
    50
    90,100
    100 65
    96
    70
    60 All tested catalysts are obtained using the impregnation method specified in Example 2, so that they contain 5% by weight of Ti02 oxide when prepared, these balls are active. soaked gshyumin hydroxide
    They are formed by different areas of the surface in such a way that the finished catalysts also have different specific surfaces. These catalysts are tested in a sulfated state with a time of end of 80
    权利要求:
    Claims (3)
    [1]
     150 200 250 From the table. 4 requires a sufficient specific surface area, with 80 being the limit below which the yield is very low. Claims Catalyst for purifying gases from hydrogen and carbon compounds of sulfur according to Claus reaction, including active alumina and having a specific surface area from 80 to 300, characterized in that, in order to increase the activity of the catalyst, it is
    a cycle of 5 s in order to determine a conversion of 50 and with a time of 5 s and 8 s in order to determine a conversion of CS / j,.
    The results are summarized in table. five.
    Tables a5 but contains titanium dioxide in the following ratio of components, wt.%: Titanium dioxide 1-60 aluminum Else Sources of information taken into account during the examination 1.Dupuy-CrauKier. Soufre-procede catalytigue CJaus J uf o rm, Ch im, 1969, No. 74, 33-37.
    [2]
    2. Thomas G. Industrial: catalytic processes and effective catalysts. M., World 1973, p. 175179.
    [3]
    3.Patent of France No. 1570161, cl .- B 01 J, published. 1969 (prototype).
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    同族专利:
    公开号 | 公开日
    FI58727B|1980-12-31|
    NL182703C|1988-05-02|
    NL182703B|1987-12-01|
    SE417500B|1981-03-23|
    IL44519A|1976-10-31|
    DE2417092A1|1974-10-24|
    SE7703550L|1977-03-28|
    DE2417092B2|1976-11-18|
    FI58727C|1981-04-10|
    ATA294774A|1978-04-15|
    IL44519D0|1974-06-30|
    RO69554A|1980-08-15|
    IT1004181B|1976-07-10|
    FR2224203B1|1976-11-12|
    NO139157B|1978-10-09|
    AT346817B|1978-11-27|
    NO139157C|1979-01-17|
    JPS5026789A|1975-03-19|
    ES425072A1|1976-11-16|
    SE403714B|1978-09-04|
    NL7404746A|1974-10-11|
    FR2224203A1|1974-10-31|
    GB1437143A|1976-05-26|
    JPS5137912B2|1976-10-19|
    BE813436A|1974-10-08|
    NO741293L|1974-10-10|
    CA1060183A|1979-08-14|
    引用文献:
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    JPS5633139B2|1977-02-03|1981-08-01|
    FR2427844B1|1978-06-05|1980-11-14|Raffinage Cie Francaise|
    FR2481145B1|1980-04-23|1984-03-23|Rhone Poulenc Spec Chim|
    DE3143400A1|1981-11-02|1983-06-01|Mobil Oil Corp., 10017 New York, N.Y.|METHOD FOR REDUCING THE SULFUR CONTENT IN GAS FLOWS WITH ELEMENTAL SULFUR|
    FR2540092B1|1983-01-31|1986-02-21|Elf Aquitaine|CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM A H2S-CONTAINING GAS|
    JPH0428644B2|1984-08-30|1992-05-14|Mitsui Miike Kakoki Kk|
    US6962683B2|2002-07-15|2005-11-08|Research Triangle Institute|Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7312658A|FR2224203B1|1973-04-09|1973-04-09|
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