WO2008019587A1 - Procédé de protection de l'activité d'un catalyseur à microsphère par la maîtrise des conditions de calcination - Google Patents

Procédé de protection de l'activité d'un catalyseur à microsphère par la maîtrise des conditions de calcination Download PDF

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WO2008019587A1
WO2008019587A1 PCT/CN2007/002351 CN2007002351W WO2008019587A1 WO 2008019587 A1 WO2008019587 A1 WO 2008019587A1 CN 2007002351 W CN2007002351 W CN 2007002351W WO 2008019587 A1 WO2008019587 A1 WO 2008019587A1
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calcination
catalyst
microsphere catalyst
microsphere
controlling
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PCT/CN2007/002351
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French (fr)
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Peng Tian
Zhihui Lv
Zhongmin Liu
Lei Xu
Xiangao Wang
Yue Qi
Lixin Yang
Shuanghe Meng
Cuiyu Yuan
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Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium

Definitions

  • the present invention relates to a process for controlling the catalytic activity of a microsphere catalyst by controlling the calcination conditions, and the catalyst preserved by the method is applied to the conversion of an oxygenate to an olefin.
  • Ethylene and propylene are the basic organic raw materials for the modern chemical industry, and their demand will increase. Therefore, the development of new production routes is of great significance.
  • the production of low-carbon olefins such as ethylene or propylene from natural gas or coal via methanol is the most promising alternative to the naphtha route to olefins.
  • the single-series, large-scale industrialization technology for the production of methanol from natural gas (or coal) is very mature, so the research on the production of olefins from methanol has become a key technology for the production of low-carbon olefins from non-oil routes.
  • the small pore phosphosilicate aluminum molecular sieve such as SAPO-34 has good catalytic activity and selectivity for methanol conversion to olefin reaction (MTO) reaction, and is currently recognized as the best molecular sieve for MTO reaction.
  • MTO methanol conversion to olefin reaction
  • Our experimental work and some literature reports have found that the storage of calcined SAPO molecular sieves generally causes a decrease in catalytic activity in an air atmosphere or in a humid environment. In order to maintain the original catalytic activity of the molecular sieve, some special technical means are needed to treat it.
  • CN1354688A reports a method for protecting the catalytic activity of the phosphosilica molecular sieve, that is, providing a protective screen to prevent it from being The catalytic activity in the methanol conversion to olefin reaction is lowered.
  • the protective screen may be a non-aqueous liquid or gas, or may be an organic templating agent remaining in the pores of the molecular sieve during the synthesis.
  • US 4,681,864 reports that SAPO-37 is less stable and in order to protect its catalytic performance in the cracking reaction, the organic template is removed from the molecular sieve just before SAPO-37 is exposed to the reaction feed.
  • US6916965 discloses a method for protecting the acid sites of SAPO molecular sieves by adsorbing one or more nitrogen-containing organic compounds on the outer surface of the molecular sieve and desorbing the compounds before use.
  • Industrial scale methanol conversion to olefins can be carried out using a circulating fluidized bed. Suitable for such devices is a microspherical catalyst having a certain particle size distribution and strength. Simple molecular sieves are difficult to form microspheres with a certain strength, and it is necessary to add an auxiliary agent, a binder such as clay, etc. to form. In addition, the active component of the catalyst should also be diluted from the thermal effects of the reaction to avoid violent exotherms.
  • the active component of the methanol-to-olefin conversion catalyst is 20-50% by weight of small pore phosphosilicate aluminum molecular sieves (such as SAPO-17, -18, -34, etc.), and the remaining components are binders, additives. Wait.
  • small pore phosphosilicate aluminum molecular sieves such as SAPO-17, -18, -34, etc.
  • the method provides a preserved microsphere catalyst which can be stored at room temperature for a long period of time.
  • the technical solution of the present invention is to provide a method for controlling the catalytic activity of a microsphere catalyst by controlling the calcination conditions, which obtains a preservation by strictly controlling the calcination atmosphere, calcination temperature, heating rate and calcination time of the microsphere catalyst.
  • the microsphere catalyst, the preserved microsphere catalyst can be stored at room temperature for a long time, and can be used after being calcined and activated in air or an oxygen-containing atmosphere before the catalytic reaction.
  • the present invention relates to a method for controlling the catalytic activity of a microsphere catalyst by controlling calcination conditions, characterized in that microspheres capable of being stored at room temperature for a long time are obtained by controlling the calcination atmosphere, calcination temperature, heating rate and calcination time of the microsphere catalyst.
  • a catalyst wherein the calcination atmosphere is nitrogen, water vapor, carbon dioxide, helium, argon or a mixture thereof; the calcination temperature is 300-7000 C; the calcination heating rate is 0.2-5 Q C / mi n; The high temperature constant calcination time is 0.2-5 h.
  • the method, the microsphere catalyst is prepared by mixing small pore SAPO molecular sieve raw powder, pore forming agent, binder and auxiliary agent, rubber grinding, and spray drying method.
  • the method refers to a silicoaluminophosphate molecular sieve having a pore diameter of less than 0.5 nm and their corresponding transition metal molecular sieves.
  • the method refers to an organic compound, preferably a natural product such as tianjing powder or starch.
  • the calcination atmosphere, the calcination temperature, the heating rate, and the calcination time of the microsphere catalyst are strictly controlled, and the calcination atmosphere is nitrogen, water vapor, carbon dioxide, helium, argon or a mixed gas thereof;
  • the baking temperature is 300-700 Q C, preferably 400-600 Q C;
  • the calcination heating rate is OJ ⁇ C/min, preferably 0.5-2 Q C/min;
  • the high temperature constant calcination time is 0.2-5 h, preferably 0.5-2 h.
  • the gas flow rate when the microsphere catalyst is calcined is 0.1-20 ml/g « ⁇ /min, preferably 0.5-10 ml/g catalyst/min.
  • the same calcination atmosphere is lowered to room temperature to obtain a retained microsphere catalyst.
  • the preserved microsphere catalyst can be calcined and activated at 500-800 ⁇ for 2-8 hours in air or a calcination atmosphere containing 5-80% oxygen before the catalytic reaction.
  • the method, wherein the preserved microsphere catalyst can be calcined in situ in a regenerator of a circulating fluidized bed apparatus for oxygenate conversion, or may be non-in situ calcined.
  • the method after calcination activation of the preserved microsphere catalyst, has an activity and selectivity for conversion of an oxygenate to an olefin similar to a fresh calcined catalyst.
  • the catalytic active center in the microsphere catalyst can be passivated by strictly controlling various parameters of the calcination process, such as calcination atmosphere, calcination temperature, calcination time, etc., to obtain a preserved microsphere catalyst, thereby realizing the catalyst. Save for a long time.
  • the stored catalyst is calcined and activated to have an oxygenate conversion to olefin reactivity and selectivity similar to that of the fresh calcined catalyst.
  • the microsphere catalyst was raised from room temperature to 500 Q C (l ° C/min) under a nitrogen atmosphere of 1 ml/g ffira /min, and maintained at this temperature for 0.5 h, and then cooled to room temperature under a nitrogen atmosphere to obtain a preserved state micro
  • the ball catalyst is referred to as BS34-1.
  • the carbonaceous catalyst is stored in an open container at room temperature. Comparative example 1
  • microsphere catalyst was raised from room temperature to 600 Q C (3 Q C/ min ) in an air atmosphere, and maintained at this temperature for 5 hours, and completely contained to remove the contained organic matter, which was designated as WB34.
  • the fully calcined catalyst was placed in an open container for storage.
  • Microsphere catalyst at lml/g The temperature was raised from room temperature to 450 Q C (0.5 ° C/min) under a nitrogen atmosphere, and maintained at this temperature for 1 h, and then the temperature was lowered to room temperature under a nitrogen atmosphere to obtain a preserved microsphere catalyst, which was designated as BS34-2.
  • the carbonaceous catalyst is stored in an open container at room temperature.
  • Example 3 Methanol conversion to olefin reaction
  • Reaction conditions A fixed bed reactor, 2.5 g of a 20-40 mesh particulate catalyst sample, was first activated by a nitrogen gas at 550 ° C for 1 hour, and then cooled to 450 Torr for reaction. The composition of the reaction product was analyzed by on-line gas chromatography using a micro pump feed, 40% methanol aqueous solution, methanol weight space velocity 2.0 h.
  • Example 1 and Example 2 were allowed to stand for 400 days, and then calcined and activated at 600 fl C for 5 hours in an air atmosphere to obtain an oxygenate-converted olefin-reactive catalyst, which was designated as BS34-1-400 and BS34-2-, respectively. 400.
  • the freshly calcined catalyst in Comparative Example 1 and the samples stored for 30 days were designated as WB34-0 and WB34-30, respectively.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Description

一种控制焙烧条件保护微球催化剂催化活性的方法
技术领域
本发明涉及一种控制焙烧条件保护微球催化剂催化活性的方法， 该方法保存的催 化剂应用在含氧化合物转化制烯烃反应。 背景技术
乙烯和丙烯是现代化学工业的基本有机原料，其需求量将越来越大。因此， 开发新 的生产路线具有十分重要的意义。 天然气或煤经由甲醇制乙烯、 丙烯等低碳烯烃是最 有希望替代石脑油路线制烯烃的工艺。 天然气 （或煤） 制取甲醇的单系列、 大规模工 业化的技术已十分成熟， 所以由甲醇制取烯烃的研究成为非石油路线制取低碳烯烃的 关键技术。
小孔磷硅铝分子筛如 SAPO-34对甲醇转化制烯烃反应 （MTO ) 反应具有良好的 催化活性和选择性， 是目前公认的用于 MTO 反应的最佳分子筛。 但是， 我们的实验 工作和一些文献报道均已发现， 焙烧型 SAPO分子筛存放在空气气氛中或湿度较大的 环境中一般会引起催化活性的下降。 为了使分子筛能保持原有的催化活性， 需要采用 一些特别的技术手段对其进行处理， 如 CN1354688A报道了一种对磷硅铝分子筛催化 活性的保护方法， 即提供一种保护屏来防止其在甲醇转化制烯烃反应中的催化活性降 低， 该保护屏可以是非水的液体或气体， 也可以是合成过程中留在分子筛孔道内的有 机模板剂。 US4681864报道了 SAPO-37的稳定性较差， 为了保护其在裂化反应中的催 化性能，在 SAPO-37即将接触反应原料之前，从分子筛中除去有机模板剂。 US6916965 公布了一种保护 SAPO分子筛酸性位的方法， 即使用一种或多种含氮的有机化合物吸 附在分子筛的外表面， 使用前将这些化合物脱附即可。
工业化规模的甲醇转化制烯烃反应可采用循环流化床， 适用于此类装置的是具有 一定粒度分布和强度的微球状催化剂。 单纯的分子筛很难形成具有一定强度的微球， 需要加入助剂、 粘结剂如粘土等才可以成型。 另外， 从反应的热效应上考虑也应该对 催化剂的活性组分进行稀释， 以避免剧烈的放热现象。 从目前公开的专利来看， 甲醇 转化制烯烃催化剂的活性成分为 20— 50wt%小孔磷硅铝分子筛 (如 SAPO-17, -18， -34 等)， 其余成分为粘结剂， 助剂等。 在实验室进行的研究中， 催化剂从焙烧到使用一般不存在时间延误问题， 可以保 证催化剂发挥其本身的最佳催化活性。 但真正的工业生产中， 催化剂从焙烧， 存储， 运输到最后装入反应器使用一般会消耗较长的时间， 并且在储运过程中为了保证产品 的品质， 也需要进行较为严格的操作和管理。 一旦中间某个环节出现问题， 将有可能 耽误工厂生产的进程， 引起不必要的损失。 因此， 寻找有效的保护催化活性的方法， 降低催化剂在储运过程中的风险是十分有必要的。 发明内容
本发明的目的在于提供一种控制焙烧条件保护微球催化剂催化活性的方法， 该方 法所得一种保存态微球催化剂， 可以在室温下长时间保存。
为达到上述目的，本发明的技术解决方案是提供一种控制焙烧条件保护微球催化 剂催化活性的方法， 其通过严格控制微球催化剂的焙烧气氛、 焙烧温度、 升温速率和 焙烧时间， 获得一个保存态微球催化剂， 该保存态微球催化剂可以置于室温长时间保 存， 用于催化反应前在空气或含氧气的气氛中焙烧活化后， 即可使用。
本发明涉及一种控制焙烧条件保护微球催化剂催化活性的方法，其特征在于，通 过控制微球催化剂的焙烧气氛、 焙烧温度、 升温速率和焙烧时间， 获得能够在室温下 长时间保存的微球催化剂， 其中所述焙烧气氛为氮气， 水蒸气、 二氧化碳、 氦气， 氩 气或它们的混合气体； 所述焙烧温度为 300-7000C; 所述焙烧升温速率为 0.2-5QC/min; 所述高温恒定焙烧时间为 0.2-5h。
所述的方法， 其所述微球催化剂， 是将小孔 SAPO 分子筛原粉、 造孔剂、 粘结 剂及助剂混合， 胶磨， 经喷雾干燥方法制备的。
所述的方法， 其所述小孔 SAPO分子筛， 是指孔径小于 0.5nm的磷酸硅铝分子 筛以及它们相应的含过渡金属分子筛。
所述的方法， 其所述造孔剂， 是指有机化合物， 优选天然产物如田菁粉或淀粉。 所述的方法， 其所述通过严格控制微球催化剂的焙烧气氛、焙烧温度、升温速率 和焙烧时间， 其焙烧气氛为氮气， 水蒸气、 二氧化碳、 氦气， 氩气或它们的混合气体； 其焙烧温度为 300-700QC， 较佳为 400-600QC;
其焙烧升温速率为 OJ^C/min, 较佳为 0.5-2QC/min;
其高温恒定焙烧时间为 0.2-5h, 较佳为 0.5-2h。
所述的方法，其所述微球催化剂焙烧时的气体流速为 0.1-20 ml/g «^/min， 较佳 0.5-10 ml/g催化剂 /min。
所述的方法， 其所述通过严格控制微球催化剂的焙烧气氛、焙烧温度、升温速率 和焙烧时间的焙烧后， 在同样的焙烧气氛下降至室温， 即得到保存态微球催化剂。
所述的方法， 其所述保存态微球催化剂用于催化反应前， 在空气或含 5-80%氧 气的焙烧气氛中于 500-800^ 焙烧活化 2-8h即可。
所述的方法， 其所述保存态微球催化剂， 可以原位在含氧化合物转化的循环流化 床装置的再生器中焙烧活化， 也可以非原位焙烧活性。
所述的方法，其所述保存态微球催化剂焙烧活化后，具有与新鲜焙烧催化剂相似 的含氧化合物转化制烯烃反应活性和选择性。
本发明方法， 通过严格控制焙烧过程的各参数， 如焙烧气氛、 焙烧温度、焙烧时 间等条件可以将微球催化剂中的催化活性中心钝化， 获得一种保存态微球催化剂， 从 而实现催化剂的长时间保存。 保存态催化剂焙烧活化后具有与新鲜焙烧催化剂相似的 含氧化合物转化制烯烃反应活性和选择性。 具体实施方式
下面通过实施例详述本发明。
微球催化剂的合成实施例
将 0.67kg的硅溶胶（Si02含量为 30wt% )、 0.71kg的高岭土（水分含量为 15wt%， 灼烧后固体中 Si02含量 53wt%， A1203含量为 45wt% ) 和 0.72kg的 SAPO-34分子筛 原粉及 2.5kg铝溶胶 （A1203含量为 20wt% )顺次混合， 搅拌。 将 0.2kg的硝酸锶 (SrO 含量 49wt%)加入到 0.2kg去离子水中， 搅拌溶解， 然后将硝酸锶溶液加入到前面的混 合料浆中， 最后加入 10g的田菁粉 （用少量乙醇浸润）， 搅拌 30min。 料液过胶体磨进 行胶磨， 使得最后所得浆料中颗粒直径 70%小于 5μπι (粒度分布测试釆用丹东市百特 仪器有限公司生产的 ΒΤ-9300型激光粒度分布仪）。 浆料进行喷雾干燥 (离心式喷雾干 燥装置)。 得到的喷雾干燥产品于 650DC空气中焙烧 4h即得到含氧化合物转化制烯烃 微球催化剂。
实施例 1
微球催化剂在 lml/g ffira/min氮气气氛下从室温升至 500QC (l°C/min), 并在此温 度保持 0.5h， 然后在氮气气氛下降温至室温， 获得保存态微球催化剂， 记为 BS34-1。 含碳催化剂放置在敞口容器中室温保存。 对比例 1
微球催化剂在空气气氛下从室温升至 600QC (3QC/min)， 并在此温度保持 5h，完全 焙烧除去所含的有机物， 记为 WB34。 将完全焙烧催化剂放置在敞口容器中保存。 实施例 2
微球催化剂在 lml/g
Figure imgf000006_0001
氮气气氛下从室温升至 450QC (0.5°C/min),并在此温 度保持 lh， 然后在氮气气氛下降温至室温， 获得保存态微球催化剂， 记为 BS34-2。 含 碳催化剂放置在敞口容器中室温保存。 实施例 3 (甲醇转化制烯烃反应）
反应条件： 固定床反应器， 2.5克 20-40目的颗粒催化剂样品， 首先在 550°C下通 氮气活化 1小时， 然后降温至 450Ό进行反应。 采用微量泵进料， 40%的甲醇水溶液， 甲醇重量空速 2.0h 反应产物组成采用在线气相色谱分析。
将实施例 1和实施例 2中的保存态催化剂放置 400天后于空气气氛下 600flC焙烧 活化 5h，得到含氧化合物转化制烯烃反应催化剂，分别记为 BS34-1-400和 BS34-2-400。 对比例 1中新鲜焙烧的催化剂及保存 30天的样品， 分别记为 WB34-0和 WB34-30。
将上面的四个样品进行甲醇转化制烯烃反应评价， 结果如表 1所示。 可以看到， 采用本专利方法保存的催化剂具有与新鲜焙烧催化剂相近的催化性能， 而完全焙烧并 于室温空气气氛中存放 30天的样品催化性能明显下降。
表 1 微球催化剂的甲醇转化反应结果 *
WB34-0 WB34-30 BS34-1-400 BS34-2-400
Figure imgf000007_0001
CH4 2.69 3.75 2.15 2.47
C2H4 52.81 50.69 52.68 53.49
C2H6 0.60 0.64 0.52 0.57
C3H6 36.28 33.24 36.89 35.86
C3H8 0.86 0.70 0.75 0.72
C4+ 5.58 7.88 5.69 5.31
C5+ 1.18 1.97 1.32 1.58 c6+ - 0.13 - -
∑c2=-c3 = 89.09 83.93 89.57 89.35 反应寿命
80-100 60-80 80-100 80-100
(min)
* 100%甲醇转化率时最高 （乙烯 +丙烯） 选择性

Claims

权 利 要 求
1、 一种控制焙烧条件保护微球催化剂催化活性的方法， 其特征在于， 通过控制微球 催化剂的焙烧气氛、 焙烧温度、 升温速率和焙烧时间， 获得能够在室温下长时间保存 的微球催化剂， 其中所述焙烧气氛为氮气， 水蒸气、 二氧化碳、 氦气， 氩气或它们的 混合气体； 所述焙烧温度为 300-700 ； 所述焙烧升温速率为 0.2-5QC/min; 所述高温 恒定焙烧时间为 0.2-5h。
2、 按照权利要求 1所述的方法， 其特征在于， 所述微球催化剂， 是将小孔 SAPO分 子筛原粉、 造孔剂、 粘结剂及助剂混合， 胶磨， 经喷雾干燥方法制备的。
3、 按照权利要求 2所述的方法， 其特征在于， 所述小孔 SAPO分子筛， 是指孔径小 于 0.5nm的磷酸硅铝分子筛以及它们相应的含过渡金属分子筛。
4、 按照权利要求 2所述的方法， 其特征在于， 所述造孔剂， 是指有机化合物， 特别 是天然产物如田菁粉或淀粉。
5、 按照权利要求 1所述的方法， 其特征在于， 所述微球催化剂焙烧时的气体流速为 0.1-20 ml/g催化剂 /min。
6、 按照权利要求 1所述的方法， 其特征在于， 所述焙烧气氛为氮气， 水蒸气、 二氧 化碳、 氦气， 氩气或它们的混合气体； 所述焙烧温度为 400-600DC; 所述焙烧升温速率 为 0.5-2QC/min; 所述高温恒定焙烧时间为 0.5-2h。
7、 按照权利要求 1所述的方法， 其特征在于， 所述微球催化剂焙烧时的气体流速为 0.5-10 ml/g催化剂 /min。
8、 按照权利要求 1所述的方法， 其特征在于， 所述保存态微球催化剂用于催化反应 前， 在空气或含 5-80%氧气的焙烧气氛中于 500-800DC 焙烧活化 2-8h。
9、 按照权利要求 1所述的方法， 其特征在于， 所述能够在室温下长时间保存的微球 催化剂， 在用于含氧化合物转化的循环流化床装置的再生器中原位焙烧活化， 或非原 位焙烧活化。
10、 按照权利要求 1所述的方法， 其特征在于， 所述能够在室温下长时间保存的微球 催化剂焙烧活化后， 具有与新鲜焙烧催化剂相似的含氧化合物转化制烯烃反应活性和 选择性。
PCT/CN2007/002351 2006-08-08 2007-08-06 Procédé de protection de l'activité d'un catalyseur à microsphère par la maîtrise des conditions de calcination WO2008019587A1 (fr)

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CN115432691B (zh) * 2022-09-01 2023-08-01 天津大学 一种超亲水含氧碳材料催化剂、其制备方法及在电催化生产过氧化氢中的应用

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