• 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:
    Reaction mass containing mixed oxides of iron with one or more metals of groups IV to VII of the periodic table of the elements, wherein the mixed oxides are deposited in finely divided form on an inert refractory substrate with a high specific surface area. The invention also relates to methods for the manufacture of this reaction mass as well as the use thereof as a catalyst for the shift reaction of carbon monoxide with steam, forming carbon dioxide and hydrogen at an elevated temperature, and/or the removal of sulphur compounds from gases.
    公开号:SU1531842A3
    申请号:SU833635148
    申请日:1983-07-29
    公开日:1989-12-23
    发明作者:Йохан Якоб Ван Дер Вал Виллем；Вильхельм Гес Йон
    申请人:Вег - Газинститут Н.В.(Фирма)；
    IPC主号:
    专利说明:

    I
    (21) 3635148 / 23-04
    (22) 07.29.83
    (31) p 32 28 481.0
    (32) 07/30/82
    (33) DE
    (46) 12/23/89. Bup. Number 47
    (71) VEG - Gas Institute H.B, (NL)
    (72) Billem Johan Jacob van der Val and Ion Wilhelm Goes (NL)
    (53) 66.097.3 (088.8)
    (56) Application of the Federal Republic of Germany No. 3131257,
    cl. On 01 D 53/14, publ. 1979
    For the application of the Federal Republic of Germany No. 3116240, cl. At 01 D 53/36, published 06/09/82.
    (54) METHOD FOR CLEANING GAS FROM SULFUR COMPOUNDS
    (57) The invention relates to the purification of sulfur detachment gas. The purpose of the invention is to increase the efficiency
    sulfur absorption. Purification is carried out by passing a gas containing sulfur compounds at 300-500 ° C through a catalytically active adsorbent of the following composition, wt%: iron oxide (3+) 2.5-38.8; chromium oxide (3+) 2.5- 22.5, carrier else, or iron oxide (3+) 26.6, manganese oxide (2+) 0.96, carrier else, or iron oxide (3+) 31, 8, zinc oxide 5.3, the rest of the carrier, when the content in the adsorbent is 80-100 wt.% Metal oxides in the form of a fine dispersion with an average particle size of 10-40 nm. The carrier is silica with a specific surface area of 50-380 or gamma-alumina with a specific surface area of 30-270.
    (L
    The invention relates to methods for purifying gas from sulfur compounds using a catalytically active adsorbent containing iron oxide and a metal oxide selected from the group including chromium, manganese, zinc, and silica or gamma alumina on a carrier.
    The aim of the invention is to increase the sulfur absorption efficiency by passing gas through an adsorbent of a specific composition containing 80-100 wt.% Metal oxides in the form of a fine dispersion with a certain average particle size.
    Example 1 (Preparation of the reaction mass according to method A. Preparing the reaction mass using ferrous iron according to a known method (German patent No. 1767202). The hydroxyl ions necessary for precipitation are introduced into the solution by injection of oxygen-free NaOH.
    10 g of silicon dioxide (AEROSIL 380 U) are suspended in 500 MP of deionized water. This slurry is heated to 90 ° C for 30 minutes, and nitrogen is bubbled through to remove dissolved oxygen. After 30 minutes, the suspension is cooled to room temperature under a nitrogen atmosphere. At room temperature, 9.3 g are dissolved in this solution.
    SP
    WITH
    00
    and

    04
    315
     and 0.7 g of MnCl2 4H, jO, the pH of the solution is adjusted to 2, then the suspension is again heated to 90 ° C and, when this T8mg 1 of 15% is reached, the pH of the solution is raised by injecting a solution of mononormal sodium hydroxide to the suspension immediately The pH remains 5 until all the iron has precipitated, then the pH rises to 11. The color of the carrier with absorbed substances is white and the iron completely settles on the carrier.
    Ferrous iron is oxidized during filtration of the absorbed carrier, as a result of which the carrier with absorbed substances takes on a bluish-green color. It is carefully prom1: it is dried with deionized water and then dried at 120 ° C for 24 hours.
    After drying, the material has a reddish color. The ratio of iron to 1: 4, the iron content is 25 wt.%, Calculated on the elemental iron on the mass of silica gel carrier, the manganese content is 7.1 wt.% With respect to iron, calculated on the elemental manganese. on the total mass of elemental iron plus manganese. The mixed oxide composition has the following 1 n total composition, wt%: 26.6; MpO 0.96; Sio rest
    The X-ray diffraction study of the sample does not show the difference between reflections of manganese hydroxides or iron, but shows diffuse lines, which indicates the presence of very small particles, which is confirmed by electron microscopy,
    Example 2 (Method B), Hydroxyl ions for the precipitation of hydrated mixed oxide are obtained by a known method (German application No. 3131255) by hydrolysis of KCNO in accordance with the equation
    KCNO + NH n-20H + CO.
    Even at 35 ° C, this reaction proceeds fairly quickly. The formation of puffs in the injection pipe must be avoided. However, at the indicated temperature, the formation of bubbles does not occur. 80 g of KCNO are dissolved in 6 deionized water. Then, 80 g of finely divided silicon dioxide (registered
    trade name LEROSKP) with a specific surface of 380. The temperature is raised to 38 ° C. 270 g of Fe (NO,) is dissolved in two liters of deionized water. 9H20 and 22 g of Cr (NO,),. This solution is injected below the surface of the vigorously stirred suspension through two injection pipes. The injection of these two liters of solution lasts 26 hours. During the injection, the pH value remains in the range of 5.2-6. 0, The precipitate is filtered, washed and dried at 12 :) C, Its color is light brown. The iron content of 46.8 wt.% Is calculated on the basis of elemental iron by the weight of the silica gel (SiO) carrier. The chromium content of 7.11 wt. calculated on the elemental chromium on the weight of elemental iron plus chromium. The total composition of the mixed oxide KONmo3Hnnn, May.7 ,: 38.8, 3.0; SiO rest. 80% of the catalyst particles have an average particle size of less than 10 nm.
    PRI me R 3 (obtaining the reaction mass according to method C). The reaction mass is prepared according to the method known (Danish Patent Application No. 6816682). In a 1.5 liter vessel, 5.4 g of silica is suspended (AEROSIL 380 V in 500 ml of deionized oxygen-free water. This suspension is heated to 90 ° C and nitrogen is bubbled through to remove dissolved oxygen. After 30 minutes suspensions were added a solution of 8.24 g of FeCl 114112 0 and 1.53 g of 300 MP of oxygen-free deionized water.
    When the temperature of the suspension is set to 90 ° C again, it starts its homogeneous oxidation by injecting 150 ml of KNOj solution in water. The concentration of the injected solution is 7.06 g of KNO in 150 ml of water, the rate of injection is 0.77 ml per minute.
    The pH of the suspension was maintained at 5.5 by injecting a solution of 1.43 n, ammonia in water. To prevent the starting material from oxidizing, the precipitation is carried out in a nitrogen atmosphere.
    After the precipitation is complete, carry out the absorbent acid) and remove the substance from the solution and dry it at 80 ° C under vacuum. The dried mass is cut into cous-glasses with a diameter
    1 mm and burned in a mixture of oxygen - argon. The ratio of iron to silicon is 1: 3, the iron content is 30 wt.% And the ratio of iron to zinc is 5: t. Electron microscopy showed a dense homogeneous distribution of iron and zinc over the surface of the carrier.
    The mixed oxide composition has the following overall composition, wt%: 31.8; ZnO 5.3; Sio rest
    Example 4 This example illustrates the use of the reaction mass according to the invention for the removal of sulfur compounds.
    In a cylindrical reactor with a diameter of 1 cm load 2 ml of the reaction mass, which contains 0.397 g of ferric oxide, 0.029 g of chromium oxide and 0.296 g of SiO. Through the reactor with a flow rate of 50 ml / min pass a gas mixture containing,%: 1.6; CO 10; H, 13; nitrogen else. Surround speed is 1500. The test was carried out at 300, 350, 400, 450 and 500 ° C. At all temperatures, the reaction rate is the same within the experimental error (the calculated error is 1.7). However, the absorption capacity increases with increasing temperature. At 350 ° C, the atomic ratio between sulfur and iron is 1, at - about 1.4.
    For regeneration over a mass of absorbent with absorbed substances, a stream of nitrogen containing 1 vol. Of oxygen is passed at 400-450 ° C. The waste gas contains elemental sulfur and only a small amount of sulfur dioxide. The formation of sulfur dioxide can be avoided by reducing the oxygen content in the gas stream at the final stage of regeneration.
    PRI me R 5. This example illustrates the regenerability of the reaction mass.
    The same catalyst is used as in Example 4. However, before conducting the experiment on the catalyst, a stream of nitrogen containing 10% hydrogen is passed through to partially reduce the active components of the catalyst.
    After this treatment, a gas mixture containing vol.%: CO 0.5; HjO 2.5; nitrogen else at 350 ° C (amount of catalyst and apparatus are
    same as in example 4). The flow rate of LO ml / min, volumetric rate
    -one
    810 h. At 350 ° C, the conversion rate
    96%, and the reaction rate constant - 14.9. Comparative values obtained according to example 2: when the reaction rate constant
    10 3.15. This indicates that the partially reduced catalyst is more active.
    The effect of the reducing potential of the gas on the activity of the catalyst is confirmed by the fact that the activity slowly decreases when the gas stream contains, vol.%: CO 0.5; HjO 2.5, nitrogen else. After 12 hours, the water content is reoxidized with the catalyst and the conversion drops to about 10.5%. The reaction rate constant is 0.51 s. Example In the present example, the desulfurization of the same hydrocarbon fractions with a boiling point of 4 ° C is described. These hydrocarbon fractions contain significant amounts of sulfuric compounds, opraHtmecKHx. They are introduced into the installation system through a pump and heat exchangers and untreated hydrocarbons enter the jet flow reactor with a temperature between 320 and 360 ° C. Hydrogen is fed into the system. AT
    25 jet flow reactor, which is filled with a conventional hydrodesulfurization catalyst such as cobalt-molybdenum oxide, organic sulfur
    compounds are converted by hydrogen,
    40 present in the gas, in the hydrogen sulfide. Then, a mixture of hydrogen sulphide and unreacted hydrogen leaves the reactor and is fed to the desaturation section at an inlet temperature of about
    45 350 and 400 ° C.
    The gas leaving this absorption section is fed through a heat exchanger to a water condenser. It consists essentially of hydrogen and
    50 is compromised and sent to
    auxiliary reactor. After the treated hydrogen passes through an additional heat exchanger, it returns to the circulation system.
    Regeneration is carried out with a mixture of air and nitrogen.
    Heat recovery is disposed of in a heat exchanger dp heating water
    Yes, returned to the network, to the temperature of the process in the reactor.
    It may be advantageous to add a small amount of oxygen to the gas from which sulfur compounds are removed. In this case, there should be no excess of oxygen in relation to sulfur (atomic ratio). In practice, in many cases, up to 2% by volume, preferably up to 1% by volume, of oxygen is sufficient for these purposes. This causes the oxidation of part of the HjS to elemental sulfur over a reactive mass. At reaction temperatures below about 200 ° C, the sulfur remains in the peaiyiOHHofl mass. At higher temperatures, in particular above 300 ° C, sulfur is at least partially entrained in the gas flow. Therefore, appropriate facilities should be provided for the condensation of sulfur.
    Another goal of the use of the reaction mass is to reduce the S0, j and N01 (in the presence of H, so it can also be used to purify secondary gases.
    Example 7. The reaction mass used in this example is obtained according to example 1 of manufacture and production method A. A cylindrical reaction tube with a diameter of 1 cm is filled with 2 ml of the reaction mass, containing, in wt.%: 26.6; MpO 0.96, SiO the rest.
    A gas mixture is passed through the reaction mass at 400 ° C consisting of,%: 1; CO 10; E 15; nitrogen rest at a volume rate of 1500. Before the breakthrough at the exit of gas from the reactor should not be detected. After skipping, concentration grows steeply. The ratio of sulfur to iron with a breakthrough of 0.75. 100% of the catalyst particles have an average particle size of less than 30 nm.
    The regeneration is carried out with a gas consisting of nitrogen and 1.5 oxygen. The gas at the exit of the reactor contains elemental sulfur and only a small amount of sulfur dioxide. The production of sulfur dioxide can be avoided by reducing the oxygen content in the gas stream.
    Example This example is related to the behavior of the reaction mass prepared in accordance with Example 3, i.e. method C
    0
    five
    about with
    d 5
    Q
    during desulfurization. 2 ml of the reaction mass, containing, wt.%:, 31,8; ZnO 5.3; SiO the rest is placed in a cylindrical reaction tube. 100% of the catalyst particles are smaller than 40 nm.
    A gas mixture at 400 ° C consisting of 0.5; CO 10; H 15, nitrogen else. Surround speed is 1500. No gas is detected before the breakthrough in the gas exiting the reactor. After breakthrough, the HjS concentration increases steeply. The ratio of sulfur to iron at a breakthrough of 0.70.
    Regeneration was carried out at 400 ° C using nitrogen containing 1.0% oxygen. Gas, leaving the reactor, contains elemental sulfur and only a small amount of sulfur dioxide. The production of sulfur dioxide can be avoided by lowering the oxygen content in the gas stream.
    Example 9: This example describes the desulfurization properties of a sorbent consisting of iron oxide / chromium oxide on silica at 20 ° C. A sorbent is prepared in Production Example 2 (method C) using 65 g Fe (NO) 9 , 7.8 g Cr (NO,) ,, - 9Н20 90 g of finely divided silica with a specific surface area of 380. This adsorption mass consists of 10 wt.% Iron oxide / chromium oxide on silica, Fe / Cr ratio 9: 1. The composition of the absorbent, wt.%: SiO 90; iron oxide 9; chromium oxide 1.
    The average particle size of iron oxide / chromium oxide is 1 nm. A cylindrical reactor with a diameter of 1 cm is loaded with five grams of absorption mass (1032 ml). The reaction gas to be desulfurized consists of 2,000 ppm, 2% water and the rest is nitrogen. The transfer rate during desulfurization is 5000 h (850 MP / min).
    No absorption is detected in the outlet gas of the reactor. After the breakdown, the sulfur / iron ratio was 1.5. During regeneration at 20 ° C, elemental sulfur was obtained, which forms a precipitate on the surface of the sorbent. When regeneration takes place at elevated temperature, elemental sulfur evaporates and collects
    in the sulfur condenser downstream of the absorption reactor.
    Similarly, catalytic adsorbents of the following composition are obtained, wt.%: A) chromium oxide 22.5; iron oxide 2.5; silica rest; b) chromium oxide 2,5; 22.5 iron oxide 22.5; dioxyg flint the rest.
    100% of the catalyst particles have a size less than them.
    Example 10. This example describes the desulfurizing properties of sorben20
    25
    the one consisting of iron oxide / hydroxy (in Example 11) is used in the desulfurization processes at 300-500 ° C. A 1 cm reactor is used. The process gas contains 6000 ppm, 10% by volume of hydrogen, 2% by volume water and the rest nitrogen. The content of iron oxide / chromium oxide. 10 wt.%. and the ratio of Fe: Cr 9: 1. During the absorption in the output gas of the reactor H S is not detected. After absorption, the ratio of sulfur to iron is about 1.0. Regeneration with oxygen at 20 ° C gives elemental sulfur. At higher temperatures, elemental sulfur is removed from the absorbent form sulfur vapor. When the regeneration is performed at gently 300 €, in the outlet gas of the reactor 50 is not detected.
    Example 13. Example 11 and 12 are carried out using an absorbent consisting of iron oxide / chromium oxide on silica. The raw materials and amounts for the preparation of the absorbent are the same as in Example 9, except that the carrier.
    yes chromium on silica, at 20 ° C. The sorbent was prepared from the same starting materials and colloids as in Example 9, except that the specific surface area of the silica mass was about 50. This absorption mass consists of 10% by weight of iron oxide / chromium oxide on silica, Fe / Gr ratio 9: 1. The composition of the absorbent, wt.%: SiO 90; iron oxide 9; chromium oxide 1.
    The average particle size of iron oxide / chromium oxide is 1 nm. A 1 cm diameter cylindrical reactor was loaded with five grams of absorption mass (10.7 ml). The reaction gas to be desulfurized consists of 2000 ppm, 2% by volume of water, 10% by volume of hydrogen and the rest is nitrogen. The transmission rate during the desulfurization of 5000 (850 ml / min
    When absorbing C1i in the output gas of the reactor does not detect. After the breakdown, the ratio of sulfur to iron would be30

    lo 1.5 During regeneration at 20 ° C, used for the absorbent, elemental sulfur is obtained in this, which forms a precipitate on the surface of the sorbent. When the regeneration is carried out at elevated temperatures, the elemental sulfur evaporates and is collected 45 in a sulfur condenser downstream of the absorption reactor.
    Example 11 The process described in Example 10 is also carried out with an absorbent which consists of JQ iron oxide / chromium oxide on gamma alumina. Absorbent prepared according to example 2, using 65 g ,,) 9HjO, 7.0 g Cr (NO,), and 90 g
    example, has a specific surface area of 100. The performance of these sorbents was comparable with absorbents for which AEROSIL 380 (380 m / g) was used (Example 2).
    Example 14. Examples 11 and 12 were carried out using an absorbent consisting of iron oxide / chromium oxide on silica. The raw materials and amounts for the preparation of the absorbent are the same as in Example 9, except that the carrier used for the absorbents is in this
    gamma-alumina, ime tsego specific, example has a specific area hf t t - f
    This surface area is approximately 270. The content of iron oxide / chromium oxide is 10%, and the ratio of Fe: Cr 9: 1. The composition of the absorbent is as follows
    surface 50 m / g. The work of these sorbents is comparable with absorbents, of which AEROSIL 380 (380) is used (example 2).
    wt.%: OKS1Shch aluminum 90; iron oxide 9; chromium oxide 1. The reactor is loaded with five grams of such an absorbent. No absorption is detected in the output gas of the reactor during absorption. After absorption, the sulfur to iron ratio was about 1.5. Regeneration with oxygen at 20 ° C takes place with the formation of elemental sulfur. At higher temperatures, elemental sulfur is removed from the absorbent as sulfur vapor.
    Example 12. Absorbent Used for Absorbent in This
    example, has a specific surface area of 100. The performance of these sorbents was comparable with absorbents for which AEROSIL 380 (380 m / g) was used (Example 2).
    Example 14. Examples 11 and 12 were carried out using an absorbent consisting of iron oxide / chromium oxide on silica. The raw materials and amounts for the preparation of the absorbent are the same as in Example 9, except that the carrier used for the absorbents is in this
    The example has a specific area PG ГТ t t - f
    surface 50 m / g. The work of these sorbents is comparable with absorbents, of which AEROSIL 380 (380) is used (example 2).
    Example 15. Examples 11 and 12 were carried out using a sorbent consisting of iron oxide / chromium oxide on alumina. The sorbent used in this example is prepared from the same starting materials and quantities as in example 11, except that oxy, aluminum has a specific surface area of 30. The absorption mass consists of wt.%: Alumina 90, iron oxide 9; chromium oxide 1. The work of this sorbent is comparable with the absorbent used in examples 11 and 12.
    Example 16 (comparative). The catalyst is prepared by the wet impregnation method. The solution containing iron nitrate (ill), chromium (III) nitrate and SiO in water is heated to. After evaporation of the water, the catalytic mass is dried at 400 ° C for activation. Thus prepared catalyst contains, wt%: Fe20j38.8; 3; SiOj else (i.e., the catalyst contains,, and SiO in the same concentrations as the catalyst of the invention obtained in Example 1).
    The catalyst obtained by the method of the application of HGF is used as described for absorption from a reducing gas containing,%: H 30; 0.32, nitrogen else. At the end of the absorption process, the HgS / sorbent (catalyst) ratio is 0.5, as opposed to the value of 0.8 reached on the sorbent in Example 1. Capacity after the second cycle
    cc

    ten
    31842 2
    desulfurization decreases by 40% to a ratio H 3 / sorbent 0.335.
    During regeneration, only SiOg is detected in the exhaust gas.
    权利要求:
    Claims (1)
    [1]
    The particle size in the catalyst obtained by the application of HGF: 95% of the particles have a size significantly greater than 40 nm. Invention Formula
    The method of gas purification from sulfur compounds by passing a gas containing sulfur compounds through a catalytic active adsorbent containing iron oxide and a metal oxide selected from the group including chromium, manganese, zinc, on a carrier — silicon dioxide with a specific surface area of 50-380 or gamma alumina with a specific surface area of 30-270 mChg at 300-500 ° C, characterized in that, in order to increase the efficiency of sulfur absorption, the gas is passed through an adsorbent of the following composition, wt.%:
    15
    20
    25
    thirty
    or
    Iron (III) oxide Chromium (III) oxide Support 1
    Iron (III) oxide Manganese (II) oxide Carrier
    2.5-38.8
    2.5-22.5
    Rest
    26,6
    0.96
    Rest,
    or
    Iron (III) oxide 31.8 Zinc oxide5.3
    Media Rest, when the content in the adsorbent 80-100 wt.% Metal oxides in the form of a fine dispersion with an average particle size of 10-40 nm.
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    同族专利:
    公开号 | 公开日
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    EP0100512A2|1984-02-15|
    AU559189B2|1987-02-26|
    EP0100512A3|1987-08-12|
    EP0100512B1|1991-01-16|
    ZA835539B|1984-04-25|
    JPH0456663B2|1992-09-09|
    US4629612A|1986-12-16|
    JPS5942042A|1984-03-08|
    AT59979T|1991-02-15|
    DE3228481A1|1984-02-02|
    AU1735583A|1984-02-02|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3228481A|DE3228481C2|1982-07-30|1982-07-30|
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