• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1 speeds of 3300-20000 h, 225 400s on a catalyst containing nickel or cobalt sulphides and molybdenum on a carrier-oxide alkini, differ- ent. u and so that, in order to increase the degree of conversion of carbon monoxide, use the specified catalyst, additionally containing alumina in the following ratio of components, wt.%: Nickel sulfide or 3.8-4.2 cobalt sulfide 10.7 -17.5 molybdenum Alumina 2,3-4,6 Carrier alumina Else 2. The method according to p. 1, characterized in that they use a catalyst containing alumina of the following composition, as a coO) mesh, May. %: Creme oxide, 354-0.39 sulphate 0.12-0.13 sodium i Chlorine 0.12-0.13 sodium, X) X surface area 219-231, C 0.41-0.59 p ml / g, average pore diameter of 7.1–11.3 nm and the product of the surface and bulk density during compaction is 162–196.
    公开号:SU1128822A3
    申请号:SU742014807
    申请日:1974-04-11
    公开日:1984-12-07
    发明作者:Рэмсботам Джон
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing an enriched hydrogen gas by converting a gas containing carbon monoxide and hydrogen sulfide with steam and can be used in a process for producing hydrogen. A known method for obtaining a gas enriched with hydrogen is by conveying a gas containing carbon monoxide in the presence of water. a pair of pr the volume ratio of steam: gas, equal to 0.5-10.0: 1, a pressure of 13.5-102.0 atomic velocity. 300-30000 pr 330-550 ° С on a catalyst containing compounds of metals VIII, VI-B and hydrocarbon groups with or without a carrier. For example, a catalyst of composition, May, is used. %: Oxide 0.1-10 cobalt Molybdenum oxide /; 0 alumina Else that can be sulphided j However, as a result of the single-stage passage of the gas mixture (conversion only 62.2% by volume), additional conversion of the gas is required. The closest to the invention to the technical essence and the achievable effect is a method of producing a gas enriched with hydrogen by converting a gas containing carbon monoxide and hydrogen sulfide, in the presence of water vapor at a molar ratio of steam: gas equal to 1.35: 1, a pressure of 1-31 atm, a space velocity of 3300-20000 h--, 225-400 ° C on a catalyst containing nickel or cobalt and molybdenum sulphides on the nose of body-alumina in the following ratio of components, wt.%: Nickel sulphide or 1 4-4.4 cobalt Molybdenum sulfide11, 2-40.0 Carrier alumina Remaining At the same time, certain requirements are imposed on the carrier, aluminum oxide: the chemical composition of the sulfate and chloride content is less than 0.1 May. % and to the surface structure - the area is more than 150 and the pore volume is more than 0.3 ml / g pj. The disadvantage of this method is that the degree of conversion of carbon monoxide is not high enough, namely, depending on the Nature of alumina used as carrier, the residual content of carbon monoxide in the gas to be converted at 225-250 ° C is, for example, 0.4-1.4 about. catalyst particles with a size of 0.2–0.6 mm at a molar ratio of steam: gas of 1.35: 1, pressure of 31 atm, with a gas feed rate of 3300 or 225–300 s. An increase in the content of sulfate or sodium chloride in the carrier, a decrease in the surface area causes an increase in the residual content of carbon monoxide. The purpose of the invention is to increase the degree of conversion of carbon monoxide. This goal is achieved in that according to the method for producing a gas enriched with air by converting a gas containing carbon monoxide and hydrogen sulfide in the presence of water vapor at a molar ratio of steam: gas equal to 1.35: 1, a pressure of 1-31 atm, space velocity of 3300-20000, 225-400 ° C on a catalyst containing nickel or cobalt sulphides and molybdenum on an alumina carrier; this catalyst is used, in addition. but containing alumina in the following ratio of components,.:.;. wt.%: Nickel or cobalt sulfide, 2 Sulfide 10.7-17.5 molybdenum Oxide 2,3-4,6 aluminum Carrier -, -, alumina Else And using a catalyst containing as a carrier alumina of the following composition, wt .%: Silicon oxide 0, 354-0.39 Sulfate 0.12-0.13 sodium Sodium chloride 0.12-0.13 surface area 219-231 m / g, pore volume 0.41-0.59 ml / g , the average pore diameter is 7.1–11.3 and the product of the surface and bulk density during compaction 162-196. The use of the invention allows to obtain a positive effect for. by increasing the degree of conversion, the content of carbon monoxide in the gas decreases to 0.3-0.6 vol.% versus 0.4-1.4 vol.% by a known method (Experimental conditions are similar). Predg catalysts are prepared. by the method of impregnation of alumina (Table 1) in one or several stages, with one or several solutions of the compounds of nickel and cobalt, mlibden, and subsequent drying and calcining of the composition. If the impregnation is carried out in several stages, then the material can be bent and fired by the intervals between successive j impregnation stages. Drying and roasting are carried out at temperatures and C, respectively. For the preparation of such catalysts, the method of dry impregnation is very convenient. In this case, the carrier is in contact with an aqueous solution of CaI combining the desired metal, and the volume of the solution exactly corresponds to the available pore volume of the impregnated carrier. The proposed catalysts are used in sulphide form. Sulfidation can be carried out using conventional methods for the sulfiding of catalysts, for example, when treating catalysts with such gases containing sulfur as a mixture of hydrogen and hydrogen sulfide, a mixture of hydrogen and carbon black or hydrogen and mercaptan, for example, butyl mercaptan. Sulfidation can also be carried out by treating the catalyst with hydrogen and a sulfur-containing hydrocarbon fraction, for example, sulfur-containing kerosene or gas oil. A sulfiding process is suitable for the catalysts of this invention, therefore it is slowly heated in a mixture of hydrogen, hydrogen sulfide and steam to a temperature in the range of 325-375 ° C, followed by a 224 temperature for some period of time. To ensure the preservation of the sulfide form of the catalyst during the reaction of varying the ratio of carbon monoxide and hydrogen in an aqueous gas, a gas containing carbon monoxide and at least 10 parts by weight of sulfur per million parts is used. This amount of sulfur is usually contained in a gas containing carbon monoxide. Otherwise, it is desirable to add a small amount of sir to the gaseous carbon monoxide continuously or periodically during the conversion. The hydrogen-rich gas obtained is further purified to produce pure hydrogen. If the cheese is a gas mixture, select from. the combustion reactor contains sulfur and / or soot, provided that sulfur and / or soot are not removed before the reaction, the syringes are only partially removed, these impurities are necessarily removed from the hydrogen-rich gas; In addition, additional purification of the hydrogen-rich gas is performed while removing carbon dioxide .. a, which is formed and not transformed during the reaction. Example 1. Preparation of catalyst I: 8.8 g of (NH) 4H20 is dissolved in 22 ml of water; 10.4 g of Ni (NO) is dissolved in 10 ml of water; 25.0 g of A1 (NO) 9H20 are dissolved in 39 ml of water. The solutions are combined and the resulting solution is impregnated with 60 g of AlnO. The impregnated alumina is dried at and fired at 500 ° C. Example 2. Preparation of catalyst II: 3.7 g of (NH) 4H20 is dissolved in 3.5 t tnHjOg; 4.3 g of Ni (NOg) is dissolved in 4 MP of water; 10.4 g of A (N0) i are dissolved in 17 ml of water. Combine the solutions and add water to make a 35 ml solution. 25 g of AljO-j are impregnated with 35 ml of solution. The impregnated alumina is dried at 120 ° C and fired at. Example 3. Preparation: Catalyst III: 8.69 g of NiCNO) is dissolved in 5 ml of water; 10.5 g of A1 (NO) 29H20 are dissolved in 17 ml. water; 7.4 g (NE.) F Ho-fO EJ O is dissolved in 8 ml. The solutions are combined and the resulting solution is taken in 50 g of Al20. 11 Alumina alumina is dried at 120 ° C and is calcined at. Example 4. Preparation of catalyst IV: 18.4 g (NH4) AHjO is dissolved in 15 ml of 21.6 g of Ni (NOo) and dissolved in 10 ml of H.0; 34.7 g CABG), dissolved in 55 ml. The solutions are combined and the resulting solution is 125 g. The impregnated drink alumina is dried at and fired at 500 ° C. Example 5. Preparation of a catalyst: 8.32 g of Ni (NO) 2 bNzO is dissolved in its crystallization BOjje by heating it to 20.1 g of Al (NO) j. dissolved in 20 md-water at 80 ° C. Both solutions are combined and water is added to make a volume of 25 ml. 48 g of Al220 ,, are impregnated with this solution and the impregnated aluminum mixture is dried at 10 ° C. Then, 7.1 g (. Dissolved in 23 ml of water. Impregnated and dried aluminum oxide is now again impregnated with the last solution, after which it is dried again at 120 ° C and roasted at 500 ° C. Example 6. Preparation for a Valliator 8.7 g of NKNO j T-dissolved in 7 ml of water; 10.5 g of A1 (NO); 9H20 dissolved in 16 ml of water; 7.4 g of (W) Mo 0244H20 dissolved in 7 ml. combined and impregnated with a total solution of 50 g of Al 2 O. Impregnated alumina is dried at 120 ° C and fired with Example 7. Preparation of catalyst VII: 20.8 g of Al (N05) -j99H20 dissolved in 32 ml of water; 14.9 Ni (NOi) 2 dissolved in 15 ml of water; 16.4 g (W4) of Mo 0244H20 dissolved in 17 ml of HjO. The pactors are combined and water is added to a total volume of 75 ml. 75 g of A1jO are impregnated with the resulting solution and the aluminum impregnated with OXIDE is dried at and baked at 500 ° C. Example 8. Preparation of catalyst VIII: 16.7 g of A1 (W,.) - 9H20 and 8.68 g of NKNOj) bN is dissolved in 35 ml of water; 15.07 g of (NH /) Mb702 4H20 are dissolved in 15 ml and the solutions are combined. 60 g of AT with a saturated solution are fed and the impregnated alumina is dried at t20 ° C and fired at. Example 9. Preparation of Catalyst IX: 17.4 g Co (NO) 2i 14.8 g (HH4) - 4H20 and 42 g of Al (NO) 9H20 are dissolved in 60 ml of water. Soak 100 g of this solution. After impregnation, the material is dried at 120 ° C and fired at 500 ° C. Example 10. Preparation of catalyst X: 6.93 g of Ni (NO) 2 and 16.69 g of A1 (NO) 9H20 are dissolved in 34 ml of water and 40 - Al20 is impregnated with this solution, after which the impregnated Al20 is dried at 120 ° C. The solution: 5.89 g (W4) b of Mo 0244H20 in 33 ml of water. Dried impregnated with the last solution, after which it is dried at 120 ° C and subjected to inspection at 500.0. Example 11. Preparation of catalyst X1: 4.3 rNiCNO and 5.2 g A1 (NO) s 9H20 are dissolved in 30 ml of water. 25 g of impregnated solution are impregnated with this solution, after which, the composition is dried at 120 C. Dissolve 3.7 g of (NH4) 6MOfOj 4Н20 in 3.5 ml of Н202, and 5 ,. A1 (NO) -91120 is dissolved in 20 ml of water, after which both solutions are combined and water is added to obtain 30 ml of the latter solution. The dried composition is impregnated; This solution, after which the impregnated composition is dried at 120 ° C and is calcined at. And Example 12, Preparation of Catalyst XII: 4.3 g of NKNOAbH O and 3.1 g of A1 (NO) are dissolved in 30 ml of water. Impregnate 25 g of ACL with this solution, after which the composition is dried at. 3.7 g of (NH.4) Mor024-4H20 is dissolved in 3.5 ml of 02 and 7.3 g of A1 (NO) 9H20 is dissolved in 20 ml of water, after which both solutions are combined and water is added to obtain 30 ml of the last solution. The dried composition is impregnated with the last solution, after which the impregnated composition is dried at and fired at. EXAMPLE 13 Preparation of Catalyst XIII: 10.4 gА1 (LОru9N is dissolved in 25 ml of water and 25 g of AIn is impregnated with this solution, then dried at. Dissolve 3.7 g (Nll Ho-f0 4-EO in 3.5 m HgO. Dissolve 4.3 NiCNO,) in 10 ml of water. Both solutions are combined and water is added to obtain a volume of 20 ml. The dried alumina is impregnated with the last solution, dried again at 120 ° C and roasted at 500 ° C Example 14. Preparation of Catalyst Catalyst: 4, Ni (NO, dissolved in 30 ml of water and impregnated with this solution with 25 g, then dried at 120 ° C. Dissolve 3.7 g of (NH) g in 3 , 5 ml H20, and in 10.4 g, A1 (NO) .9 is dissolved in 16.4 ml of water. Both solutions are combined and the dried composition is sprayed with a common solution, after which the composition is dried at 12 ° C and calcined at 500 ° C. Example 15 Preparation of Catalyst XV: 17.34 g NiCNO), bN 14.72 g (III) bMou024-4H20 and 69.52 Al (NOp ,. dissolved in 100 ml of water. 100 g are impregnated with this solution and then aluminum oxide dried at 120 s and fired at 500 ° C. Example 16. Preparation of Catalyst XVI: 2 g of (NH) 6MO702 4H are dissolved in 12.5 ml of water; 4.33 g of Ni (NO) 2 is dissolved in 12.5 ml of water. Both solutions are combined and 25 g are impregnated with the resulting solution. The catalyst preparation is completed by drying at 120 ° C and calcining at 500 ° C. Example 17. The preparation of catalyst XVII: 5.16 g of (NH) gMo 0244H O is dissolved in 30m of water; 6.07 g of NiCNO) is dissolved in 30 ml of water. Both solutions are combined and 35 g of AlgO are impregnated with the resulting solution, after which the alumina is dried at 12 {I and calcined at 500 ° C. Example 18. Preparation of catalyst XVIII: 95.35 g Ni (NO / 3) 2 6Н20 is dissolved in 100 ml of water; 80.97 g (Nil) gMOfO H O pa is created in 225 ml of water. The solutions are combined and the resulting solution is impregnated with 550 g, after which the preparation of the catalyst is completed: they are dried by drying at 120 ° C and roasting at .500 C. Example 19. Preparation of the XIX catalyst: impregnated with 100 g of aqueous solution containing 17.4 g CoCNO) 6H20 and 14.8 g (NH4) 5Moj0244HyO. After impregnation, the material is dried at and subjected to firing at. The characteristics of the alumina used as a carrier are presented in table. 1. The compositions of the obtained catalysts are presented in table. 2. Catalyst XX- (GirdIer-G66B) contains May. %: aluminum 12.9; copper 24.0; zinc 11.6; oxygen 51.5; and catalyst XXI (Girdler-G3A) -. The characteristics of the feedstock are given in table. 3. Example 20. The original gas containing hydrogen sulfide is passed over catalyst XVI at a rate of 3 l / h with a slow increase in temperature from 20 to 350 ° G. Starting from 100 ° C, steam is supplied at a rate of 5.6 l / h. During sulphidation, the pressure is slowly increased, starting from atmospheric. The heating rate is chosen such that at a temperature of 350 ° C is reached, after about 21/2 hours. A pressure of about 10 atm, when the temperature reaches 350 ° C, is subsequently quickly increased to a working pressure of 31 atm, with the introduction of the specified gas, containing carbon monoxide. A temperature of 350 ° C is maintained for 1 hour while passing said mixture of source gas and steam over the catalyst. Then the desired temperature is set to 300 ° C and the vapor-gas mixture is passed at a ratio of 1.35 mol of steam to 1 mol of gas with a bulk velocity of 3300 l of wet gas per 1 l of catalyst per t h, the particle size of which is 0.2-0.6 mm. The content of carbon monoxide and hydrogen in the resulting dry gas is presented in table. 4. The results of using catalysts of other compositions using aluminum oxide at different temperatures and a space velocity of 9000 liters of gas flow per 1 liter of catalyst per hour (particle size 0.2-0.6 mm) are presented in table 5.
    9
    The results of testing catalysts of different compositions with the use of oxide alk 4ini at 225 ° С and a volume ratio of 9000 liters of raw gas per 1 liter of catalyst per hour (particle size 1.5 mm) are presented in table. 6, and with a bulk velocity of 20,000 l (particle size 0.2-0.6 mm) in Table. 7
    An advantage of the invention is the high resistance of the catalyst obtained to sulfur-containing compounds. So, if at conversion on the industrial catalyst Girdler8822, 10
    -G-66 V at 225-250 ° C. The residual content of carbon monoxide is 0.4-2.0 vol.%, Then during conversion
    the proposed method is 0.35 0.4% by volume. .
    In the process of conversion in the presence of hydrogen sulfide, the industrial catalyst is deactivated, whereas the catalyst of the proposed method maintains its working capacity even with a significant content of sulfur-containing compounds both in g of the 1 st phase and using a sulfur-containing carrier.
    blitz 1
    T a
    Aluminum oxide
    0.41
    1 2 3
    0.59
    0.52
    Continuation of table 1
    7.1
    196 10.3 164
    11.3 162 Ni, S. 3.93.9 4.0 3.9 COgSg 10.7 10.7 11.0 10.9 4.64.6 2.3 3.1 Carrier oxide AlOsal Mini Impurities in the composition of the carrier, wt.% SiOj0.37 , 1.38 0.36 0.37 0.12 0.1260.12 0.12 NaCl0.12 0.1260.12 0.12 3.9 3.9 3.9 3.9 3.9 3.8 4.1 4.1 - - .- --10, 7 10.7 10.7 10.7 10.7 10.4 11.3 11.3
    4.6 4.6 4.6 4.6 4.6 4.6 7.4
    Aljo
    Continued table. 2 3.94.0 4.2 3.0 10.7 11.0 15.3 17.5 10.7 4.62.3 3.0 2.9 4.6 e 0.37 0.38 0, 39 0.37 0.37, 0.12 0.12 0.12 0.13 0.12 0.12 0.12 0.12 0.12 0.13 0.13 0.12 0.12 4.1-1.411, 3 11.2 - K m4 component Active phase - ---.-- X XI Carrier alumina Impurities in a carrier, May. % SiOj1.36 1.36 Na, 86 1.86 NaCl0.12 0.12 Components
    Carbon monoxide.
    Carbon dioxide
    Hydrogen
    Methane
    Hydrogen sulphide
    5.8
    29.4
    92
    64.1
    0.3
    0.4 Catalyst May. %: -, - iXII XIII XIV XV XVI XVII XVIII XIX The rest 1.36 1.36 1.36 0.383 0.355 1.42 0.354 0.355 1.86 1.86 1.86 0.122 0.12 1.89 0.354 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 (Gas containing Gas, containing The source gas, carbon monoxide,; stinging gray. May.% Continuation of table 2, about Table 3 I May.% Hydrogen, May.%
    -CS |
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    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING A GAS RICHED WITH HYDROGEN by converting a gas containing carbon monoxide and hydrogen sulfide in the presence of water vapor at a molar vapor: gas ratio of 1.35: 1, a pressure of 1-31 atm, and a space velocity of 3300-20000 h ' 1 , 225'-400 ° С on a catalyst containing nickel or cobalt and molybdenum sulfides on an alumina support; catalyst, additionally alumina contents in the following ratio of components, May.%:
    Nickel or cobalt sulfide 3.8-4.2
    Molybdenum Sulfide 10.7-17.5
    Alumina 2.3-4.6
    Alumina carrier Else
    [2]
    2 · Method pop. ^ characterized in that they use a catalyst containing aluminum oxide of the following composition as a carrier, May.
    Silica 0.354-0.39
    Sodium Sulfate 0.12-0.13
    Sodium chloride 0.12-0.13 surface area 219-231 m 2 / g, pore volume 0.41-0.59 ml / g, average pore diameter 7.1-11.3 nm and the product of surface and bulk weight at seal 162 - 196 m 2 / ml.
    SUm, 1128822
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    同族专利:
    公开号 | 公开日
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    引用文献:
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    FR2575453B1|1984-12-28|1990-03-02|Pro Catalyse|PROCESS OF CONVERSION OF CARBON MONOXIDE BY WATER VAPOR USING A THORORESISTANT CATALYST|
    US4892717A|1985-07-31|1990-01-09|Union Oil Company Of California|Gas treating process|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NLAANVRAGE7305340,A|NL175835B|1973-04-17|1973-04-17|Process for preparing a hydrogen-rich gas from a carbon monoxide-containing gas using a nickel and / or cobalt and molybdenum-containing catalyst.|
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