WO2007068202A1 - Production d'hydrogene par pyrolyse d'hydrocarbure avec des catalyseurs de magnesium metallique et de magnesium metallique dope avec d'autres metaux - Google Patents

Production d'hydrogene par pyrolyse d'hydrocarbure avec des catalyseurs de magnesium metallique et de magnesium metallique dope avec d'autres metaux Download PDF

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Publication number
WO2007068202A1
WO2007068202A1 PCT/CN2006/003390 CN2006003390W WO2007068202A1 WO 2007068202 A1 WO2007068202 A1 WO 2007068202A1 CN 2006003390 W CN2006003390 W CN 2006003390W WO 2007068202 A1 WO2007068202 A1 WO 2007068202A1
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WIPO (PCT)
Prior art keywords
reaction
hydrogen
catalyst
metal magnesium
produce hydrogen
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PCT/CN2006/003390
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English (en)
Chinese (zh)
Inventor
Ke Wang
Wensheng Li
Xiaoping Zhou
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Microvast Technologies, Ltd.
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Publication date
Application filed by Microvast Technologies, Ltd. filed Critical Microvast Technologies, Ltd.
Publication of WO2007068202A1 publication Critical patent/WO2007068202A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts

Definitions

  • the present invention discloses a process for catalytically decomposing hydrocarbons to produce hydrogen from a mixture of metallic magnesium and its doped other metals.
  • Keiichi Tomishige [Energy & Fuels 2001, 15, 571-574] reported that nickel is supported on alumina to react with water vapor to produce hydrogen, and carbon monoxide and hydrogen are produced at 800 ⁇ 1100: °0.
  • Giuseppe Barbieri [Ind. Eng. Chem. Res. 2001, 40, 2017-2026] reported steam reforming on a palladium membrane reactor and theoretically analyzed the model of the reaction. In the partial oxidation of methane, formamidine reacts with oxygen to form carbon-containing compounds and hydrogen.
  • US5149516 and US5447705 describe the successful implementation of this reaction on perovskites at a temperature of 600-900 ° C and a pressure of 0. IMPa.
  • U.S. Patent No. 4,973,486 discloses the use of hydrogen bromide as a catalyst for the reaction of methane with oxygen at 850 Torr to produce carbon monoxide, hydrogen, ethylene and acetylene. After completion of the reaction, the amount of hydrogen bromide remains unchanged.
  • Korada Supat [Ind. Eng. Chem. Res. 2003, 42, 1654-1661] Using a ring current to energize, a partial oxidation reaction and a steam reforming reaction occur simultaneously, and good results are obtained.
  • the product inevitably contains environmentally harmful carbon oxides, particularly carbon monoxide, which, although separated, are difficult to remove.
  • concentration of carbon monoxide in the pure hydrogen gas required for the fuel cell cannot exceed 20 ppm. Therefore, the hydrogen produced by the reforming of the formazan cannot be directly used for the fuel cell, and the carbon monoxide must be removed by secondary separation to reduce the carbon monoxide to the level of 20 ppm. It requires complicated processes and a lot of energy.
  • U.S. Patent No. 4,064,740 discloses a method of directly thermally cracking water which is simple in material and which decomposes water directly at high temperatures. However, the reaction requires a high temperature of over 2000 , which requires a huge amount of energy.
  • U.S. Patent No. 4,024,230 describes the use of triiron tetroxide and chlorine as a catalyst to decompose water into hydrogen and oxygen through a catalytic cycle. This method successfully reduces the temperature of water decomposition, but requires a reactor that is expensive to withstand chlorine corrosion. .
  • U.S. Patent Nos. 5,958,297 and US Pat. No. 6,673,270 use a Group VIII metal such as nickel and cobalt as a catalyst to catalyze the reaction of hydrocarbons such as kerosene with oxygen to produce hydrogen gas. This process can treat a wide range of hydrocarbons, from carbon-based compounds to formamidine. Carbon-10 compounds such as naphthalene can react with hydrogen to produce hydrogen, but there are drawbacks such as complicated products, low selectivity, and difficulty in separation.
  • 6,059,995 and 5,837, 217 describe the use of dimethyl ether or methanol as a feedstock for steam reforming to produce hydrogen. Since the raw material price is relatively expensive, the economic benefits are not significant. In addition, the method requires oxidation of a part of hydrogen to provide heat for the reforming reaction, and also reduces the efficiency of hydrogen production.
  • U.S. Patents 4,372,833 and 4,507,185 use visible light to decompose formate and water to produce hydrogen, but are also limited by the source of the material, and the method has little application prospects.
  • the invention adopts magnesium metal and its doping Ca, Li, Na, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ge, Rb, Sr, Y, Zr, Nb, Mo , Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Tl, Pb,
  • a mixture of Bi, La, Ce and Sm as a catalyst which directly catalyzes the decomposition of hydrocarbons to produce hydrogen and carbon.
  • the reaction raw materials are hydrocarbons including anthracene hydrocarbons, olefins, alkynes, carbocyclic compounds, aromatic compounds, waste plastics, waste rubber and asphalt.
  • the catalytic reaction is carried out at 200 to 1500 ° C, 0.01 to 10 atmospheres.
  • the reactor is a bubble reactor.
  • the mixture of metal magnesium and its doped other metals is directly used as a catalyst, it can be directly added to the reactor, thereby greatly reducing the pretreatment process, saving cost and time.
  • the conditions of the reaction are selected in a wide range, especially in relatively mild conditions to obtain higher yields. For example, when methane is used as a raw material, the maximum single-pass conversion of the reaction can reach 35%, and the products of the reaction are hydrogen and carbon powder.
  • the invention is characterized in that the life of the catalyst is much greater than the reported catalyst, which can be more than 120 hours.
  • the catalyst is automatically separated from the product, which is very easy to separate, and the recovered catalyst can be reused without reducing the activity.
  • Figure 1 is a schematic diagram of a hydrocarbon catalytic decomposition unit
  • Figure 2 is a schematic diagram of a two-stage catalytic decomposition reactor for hydrocarbons.
  • Examples 1 to 5 Weigh a certain amount of metal developing agent and cocatalyst into a reactor 14 equipped with a stainless steel inner cylinder 15 closed at one end (as shown in Fig. 1) to make an intake pipe 7, a thermocouple 11 The catalyst maintains good contact and is well sealed. The reactor is then placed in a furnace 19 to adjust the height of the reactor to ensure uniform heat transfer. Connect the A-burning cylinder 1 and the reaction line, plug the rubber stopper 9, and check the leak. Adjusting the pressure reducing valve 2 through feeding, so that the air pressure reaches O.lMPa, and opening the control valve with the flow meter 3 and the display device 4 to control the flow rate of 5 ml/min. Vent for twenty minutes to ensure that other gases in the reactor are flushed.
  • the heating device comprises a temperature controller 5, a thermocouple 11, a heating component 12, 13, a heat insulating material 17, 18, etc., the temperature controller 5 is turned on, the temperature is raised to 700 ° C, and after the temperature is stabilized, at the sampling point 6 and Sampling point 8 on trachea 10 was sampled and analyzed by gas chromatography color spectrometry. After the reaction, turn off the temperature controller and stop heating. Continue to pass methane until the temperature has cooled to room temperature and stop venting. The reactor 14 was taken out from the stainless steel inner jacket 15, and the generated carbon powder was poured out and weighed. Change different procatalysts The reaction is carried out with a cocatalyst. The reaction results are shown in Table 1.
  • Example 10 4 g of the metal magnesium catalyst was weighed, and the reaction apparatus, the operation method, the reaction pressure and the flow rate were the same as in Example 1, and the reaction temperature was 68 (TC). After 20 hours of the reaction, the analysis showed The methane conversion rate remained stable at 22.0%.
  • Example 11 4 g of the metal magnesium catalyst was weighed, and the reaction apparatus, operation method and flow rate were the same as in Example 1. The reaction temperature was 700 Torr. After 20 hours of the reaction, the analysis showed that the conversion of formazan was still stable at 23.0%.
  • Example 12 4 g of the metal magnesium catalyst was weighed, and the reaction apparatus, the operation method and the flow rate were the same as in Example 1. The reaction temperature was 720 ° C, and the reaction was carried out for 25 hours, and the results showed that the conversion of formazan was still stable at 27 %.
  • Example 13 4 g of a metal magnesium catalyst was weighed. The reaction apparatus, operation method and flow rate were the same as in Example 1. The reaction temperature was 740 ° C. After the reaction was carried out for 25 hours, the analysis showed that the conversion of formamidine was still stable at 32.0%.
  • Example 14 4 g of the metal magnesium catalyst was weighed, and the reaction apparatus, the operation method and the flow rate were the same as in Example 1. The reaction temperature was 760 Torr. After the reaction was carried out for 20 hours, the analysis showed that the methane conversion rate was still stable at 31%.
  • Example 15 4 g of a metal magnesium catalyst was weighed, and the reaction apparatus, operation method and flow rate were the same as in Example 1. The reaction temperature was 700 ° C. After 15 hours of the reaction, the analysis showed that the ethane conversion rate was still stable at 62.0%.
  • Example 16 4 g of a metal magnesium catalyst was weighed, and the reaction apparatus, the operation method, the reaction pressure and the flow rate were the same as in Example 1, and the reaction temperature was 700 °C.
  • the conversion of propylene is stable at 90.0%, the selectivity of hydrogen is 80.0%, and the by-product is methane.
  • Example 17 2 g of the metal magnesium catalyst and 1 g of the pitch were weighed.
  • a two-stage reactor was used (as shown in Fig. 2, each reactor is described in detail in Example 1), at the first
  • the stage reactor is connected to the second stage reactor to further carry out the decomposition reaction. Connect the reaction line and check the leak.
  • the inert gas is passed through the inert gas for twenty minutes to ensure that other gases in the reactor are flushed.
  • the temperature control system is turned on, and the pre-stage reactor is programmed to increase temperature to 70 (TC) at a rate of C per minute.
  • samples are taken at the analysis ports 1, 2 and quantitatively analyzed by a gas chromatograph.
  • the pitch is completely decomposed and the hydrogen selectivity is More than 80.0%, the by-product is methane.
  • Example 18 2 g of a magnesium metal catalyst and 1 g of plastic rice were weighed and placed in a reactor equipped with a stainless steel inner cylinder to keep the intake pipe, the thermocouple, the catalyst in good contact, and sealed well. The reactor and heating jacket are then placed in a heating furnace to adjust the height of the reactor to ensure uniform heat transfer.
  • a two-stage reactor shown in Fig. 2 is used, and after the first-stage reactor, the second-stage reactor is connected to further decompose the reaction. Connect the reaction line and check the leak. The inert gas is passed through the inert gas for twenty minutes to ensure that other gases in the reactor are flushed.
  • the temperature control system is turned on, and the pre-stage reactor is heated to 700 ° C at a speed of 1 ⁇ per minute. During the heating process, samples are taken at the analysis ports 1 and 2 and quantitatively analyzed by gas chromatography. The plastic rice is completely decomposed and the hydrogen is selected. The property is 90.0% or more, and the by-product is methane.
  • Example 19 2 g of a metal servant catalyst and 1 g of rubber were weighed and placed in a reactor equipped with a stainless steel inner cylinder to keep the inlet pipe, the thermocouple, the catalyst in good contact, and sealed well. Then, the reactor and the heating sleeve are placed in a heating furnace, and the height of the reactor is adjusted to ensure that the heat transfer is hooked.
  • a two-stage reactor shown in Fig. 2 is used, and after the first-stage reactor, the second-stage reactor is connected to further decompose the reaction. Connect the reaction line and check the leak. The inert gas is passed through the inert gas for twenty minutes to ensure that other gases in the reactor are flushed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un procédé pour produire de l'hydrogène gazeux et du carbone par pyrolyse catalytique directe d'hydrocarbure. Selon cette invention, du magnésium métallique et du magnésium métallique dopé avec d'autres métaux sont utilisés comme catalyseurs. La réaction a lieu sous une pression située entre 0,01 et 10 atmosphères et à une température située entre 200 et 1500 °C. Une fois la réaction terminée, le catalyseur est automatiquement séparé du produit résultant et peut être remis en circulation et réutilisé. L'hydrogène gazeux ainsi obtenu ne contient aucune impureté de CO, de CO2, etc.
PCT/CN2006/003390 2005-12-14 2006-12-13 Production d'hydrogene par pyrolyse d'hydrocarbure avec des catalyseurs de magnesium metallique et de magnesium metallique dope avec d'autres metaux WO2007068202A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2005100325470A CN100439238C (zh) 2005-12-14 2005-12-14 金属镁及其掺杂其他金属的混合物催化分解碳氢化合物制氢
CN200510032547.0 2005-12-14

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WO2014144374A2 (fr) 2013-03-15 2014-09-18 West Virginia University Research Corporation Procédé pour la production de carbone pur, compositions et procédés pour ceci
CN107108215B (zh) 2014-10-21 2021-03-16 西弗吉尼亚大学研究公司 用于制造碳、碳化物电极及碳组合物的方法和装置
TW201800332A (zh) * 2016-02-01 2018-01-01 西維吉尼亞大學研究股份有限公司 由天然氣及其他烴類製造碳及氫之方法
WO2017184760A2 (fr) 2016-04-20 2017-10-26 West Virginia University Research Corporation Procédés, appareils et électrodes pour la conversion d'un carbure en carbone avec des composés chimiques nanostructurés à base de carbure
CN106556637A (zh) * 2016-11-11 2017-04-05 上海理工大学 一种光电催化反应实验装置
CN113912007A (zh) * 2021-09-13 2022-01-11 东南大学 一种利用废塑料的连续催化制氢系统及方法

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CN1291165A (zh) * 1998-02-24 2001-04-11 尼亚加拉莫霍克能量公司 通过直接裂解烃制备氢
CN1350977A (zh) * 2000-10-26 2002-05-29 中国科学院大连化学物理研究所 一种甲烷催化裂解制氢或氢烷的方法

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FR2790750B1 (fr) * 1999-03-10 2001-04-20 Air Liquide Procede et dispositif de production d'hydrogene par decomposition thermocatalytique d'hydrocarbures
US6869585B2 (en) * 2000-06-16 2005-03-22 Kiyoshi Otsuka Method and apparatus for supplying hydrogen and portable cassette for supplying hydrogen

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CN1291165A (zh) * 1998-02-24 2001-04-11 尼亚加拉莫霍克能量公司 通过直接裂解烃制备氢
CN1350977A (zh) * 2000-10-26 2002-05-29 中国科学院大连化学物理研究所 一种甲烷催化裂解制氢或氢烷的方法

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