WO2012100424A1 - 一种催化剂载体 - Google Patents

一种催化剂载体 Download PDF

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Publication number
WO2012100424A1
WO2012100424A1 PCT/CN2011/070727 CN2011070727W WO2012100424A1 WO 2012100424 A1 WO2012100424 A1 WO 2012100424A1 CN 2011070727 W CN2011070727 W CN 2011070727W WO 2012100424 A1 WO2012100424 A1 WO 2012100424A1
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similar
catalyst carrier
catalyst
spring
similar unit
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PCT/CN2011/070727
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English (en)
French (fr)
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刘艳菊
杨华
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北京市理化分析测试中心
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Priority to DE112011100158.4T priority Critical patent/DE112011100158B4/de
Priority to PCT/CN2011/070727 priority patent/WO2012100424A1/zh
Publication of WO2012100424A1 publication Critical patent/WO2012100424A1/zh

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    • B01J35/56—
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron

Definitions

  • the invention belongs to the field of catalysts, and in particular to a catalyst carrier.
  • the specific surface area is one of the important indexes for characterizing the performance of the catalyst.
  • the specific surface area is the internal (or external) surface area of 1 g of the catalyst or the catalyst support, and the larger specific surface area can increase the catalytic efficiency of the active component per unit mass.
  • the carrier is one of the components of the supported catalyst.
  • the catalytically active component is supported on the surface of the carrier.
  • the carrier is mainly used to support the active component, so that the catalyst has a specific physical property.
  • the carrier can make the prepared catalyst have a suitable shape. , size and mechanical strength to meet the operational requirements of industrial reactors; for example, the carrier can disperse the active component on the surface of the support to obtain a higher specific surface area and the like.
  • the catalyst In the field of applied catalysis, it is often required that the catalyst has a large specific surface area while the volume is small, to meet the limitation of the catalyst installation space and maximize the role of the catalyst, while the larger specific surface area and smaller volume are often not available. Also, this is a key factor affecting the application of catalysts.
  • the technical problem to be solved by the present invention is to maximize the specific surface area of the catalyst under a certain volume, thereby improving the efficiency of use of the catalyst.
  • the present invention provides a catalyst carrier formed by stacking a plurality of similar planar bodies, each of which is formed by nesting a plurality of similar unit frames, the multilayer similar unit
  • the geometry of the frame is similar to the geometry of the cross-section of each of the similar planar bodies, each of which is a spring-like helical structure.
  • the plurality of similar planar bodies are hooked and supported to form a network structure by bonding or by using a wire containing an active component or a promoter.
  • the plurality of similar units are hooked and supported to form a network structure by bonding or by using a wire containing an active component or a promoter.
  • the shape of the carrier is a combination of one or a combination of a rectangular parallelepiped, a cylinder, a vertebral body, and a sphere.
  • cross-sectional shape of the similar planar body is a combination of one or more of a rectangle, a circle, a triangle, or an ellipse.
  • the surface of the spring-like spiral structure of the similar unit frame is provided as a rough surface, or a plurality of holes are provided on the surface of the frame.
  • the spring-like helical structure of the similar unit frame is made of the active component or the catalyst material itself supported on the carrier.
  • the "body” is cut into “face”, and then the “face” is cut into “line”, and finally the “line” is converted into a spring-like spiral material "magnification” process to ensure that it does not increase.
  • the specific surface area is increased as much as possible, and at the same time, the surface area of the spring-like spiral frame is further increased by changing the roughness or providing holes, thereby further increasing the specific surface area of the carrier, thereby improving the utilization of the catalyst. rate.
  • 1a is a schematic structural view of a rectangular parallelepiped catalyst carrier according to an embodiment of the present invention.
  • 1b is a schematic structural view of a multilayer similar planar body of a rectangular parallelepiped catalyst carrier according to an embodiment of the present invention
  • Figure 1c is a schematic view showing the structure of a similar unit frame of a rectangular parallelepiped catalyst carrier according to an embodiment of the present invention
  • FIG. 2a is a schematic structural view of an elliptical columnar catalyst carrier according to an embodiment of the present invention.
  • 2b is a schematic structural view of a multilayer similar planar body of an elliptical cylindrical catalyst carrier according to an embodiment of the present invention
  • 2c is a schematic structural view of a similar unit frame of an elliptical cylindrical catalyst carrier according to an embodiment of the present invention.
  • Figure 3 is a schematic view showing the structure of a truncated-shaped catalyst carrier according to an embodiment of the present invention.
  • FIG. 4 is a schematic structural view of a spherical catalyst carrier according to an embodiment of the present invention.
  • Figure 5 is a schematic view showing the structure of a conical catalyst carrier according to an embodiment of the present invention.
  • Figure 6 is a schematic view showing the structure of a multi-layer similar planar body of a truncated cone-shaped, spherical and conical catalyst carrier according to an embodiment of the present invention
  • Figure 7 is a schematic view showing the structure of a similar unit frame of a truncated cone-shaped, spherical and conical catalyst carrier according to an embodiment of the present invention.
  • Figure 8 is a graph showing the relationship between the number of turns of a spring-like spiral structure of a similar unit frame and the removal rate of gaseous pollutants according to an embodiment of the present invention.
  • FIG. 1a-1c there is shown a schematic structural view of a rectangular parallelepiped catalyst carrier and its constituent parts according to an embodiment of the present invention.
  • the cuboid-shaped catalyst carrier is formed by stacking a plurality of layers of similar cuboids; as can be seen in Fig. 1b, each of the similar cuboids is formed by nesting a plurality of rectangular similar unit frames, that is, multiple layers.
  • Rectangular similar element frames are unequal in length and nested one by one to form a similar cuboid; as can be seen in Figure 1c, each rectangular similar cell frame is a spring-like spiral; to further increase the specific surface area
  • the frame surface of the spring-like spiral structure is provided as a rough surface or a plurality of holes are provided.
  • the elliptical cylindrical catalyst carrier is formed by stacking a plurality of similar elliptical cylinders; as can be seen in Fig. 2b, each layer of similar elliptical cylinders is nested by a plurality of elliptical similar unit frames. Forming, that is, the long-axis and the short-axis of the similar unit frame of the multi-layered ellipse are not equal to each other, nesting one by one to form a layer of the similar elliptical cylinder; as shown in Fig. 2c, the similar unit of each layer of the ellipse
  • the frame is a spring-like spiral structure; to further increase the specific surface area, the frame surface of the spring-like spiral structure is provided as a rough surface or a plurality of holes are provided.
  • FIG. 3 is a schematic structural view of a truncated cone-shaped, spherical, and conical catalyst carrier and its components according to an embodiment of the present invention.
  • Figures 3-5 show that the truncated cone-shaped, spherical, and conical catalyst carriers are formed by stacking a plurality of similar truncated, spherical, and conical cylinders;
  • Figure 6 shows a similar truncated cone shape for each layer.
  • the spherical and conical cylinders are further formed by nesting a plurality of circular similar unit frames, that is, the radius of the similar unit frames of the plurality of circular circles are not equal to each other, nesting one by one, forming a similar circular truncated cone shape, a spherical and conical cylinder;
  • FIG. 7 shows that each of the circular similar unit frames is a spring-like spiral structure; to further increase the specific surface area, the boundary surface of the spring-like spiral is set to a rough surface or a plurality of Holes.
  • the term "similar” means that the shapes of the geometric or geometrical shapes involved are the same, but the specific dimensions are not the same, similar to similar triangles, similar polygons, and the like.
  • the relationship between the number of turns of the spring-like spiral structure of the similar unit frame and the removal rate of gaseous pollutants is as shown in FIG. 8.
  • the optimal number of turns of the spring-like spiral structure is to achieve the highest removal rate. Settings.
  • the removal rate of pollutants increases first and then decreases with the increase of the number of spiral turns.
  • the optimal number of turns is determined by the number of turns corresponding to the highest pollutant removal rate. The trend of increasing first and then decreasing is due to the number of turns. More, the larger the specific surface area, but the air resistance passing through it is also enhanced.
  • a catalyst material for a pollutant component may be used to prepare a catalyst carrier, and the number of turns of the spring-like spiral structure in the catalyst carrier may be employed. Set to the optimal number of turns to achieve the highest contaminant removal rate. Therefore, according to different environments and purposes, catalyst carriers are prepared using different kinds of catalyst materials, and spring-like spiral structures of similar unit frames of different sizes and turns are provided.
  • the catalyst carrier of each of the above embodiments between the plurality of similar planar bodies and between the plurality of similar unit frames, they may be hooked by bonding, using a wire containing an active component such as activated carbon fiber or cocatalytic action.
  • the support forms a network structure.
  • the air pollutants can be purified by using various geometric catalyst carriers as shown in FIG. 1-7, for example, using a nano-fiber supported by a titanium dioxide catalyst to form a similar unit of a spring-like spiral structure, which is fabricated by the above-mentioned nesting, stacking, and the like.
  • a catalyst capable of removing benzene and formaldehyde in the air for example, a treated noble metal (such as platinum, rhodium, palladium, etc.) or a transition metal (such as iron) is formed into a similar unit of a spring-like spiral structure, through the above nesting It is made into a catalyst capable of removing nitrogen oxides in the air, etc. by stacking.
  • the above catalyst can be installed in an air purifier to improve the purification effect of related pollutants in the air.
  • the amount of pores on the surface of activated carbon determines the adsorption effect on air pollutants.
  • the large specific surface area and small volume of the catalyst carrier provided by the invention are formed by stacking a plurality of similar planar bodies, and each layer of similar planar bodies is formed by nesting multiple layers of similar unit frames, and the geometry of each layer of similar unit frames and each layer Similar geometric plane cross-section geometry is similar, each layer of similar unit frame is a spring-like spiral structure, such a structure is to "body” into a “face”, then the "face” into a “line”, and finally The "line” is converted into a spiral step-by-step amplification process to ensure that the specific surface area is increased as much as possible without increasing the volume of the catalyst carrier; at the same time, the roughness or the hole is changed on the surface of the spiral frame, and further The specific surface area of the carrier is increased to increase the utilization rate of the catalyst, so that the effect of purifying the air pollutant is better.

Description

一种催化剂载体
技术领域
本发明属于催化剂领域，具体涉及一种催化剂载体。
背景技术
比表面积是用于表征催化剂性能的重要指标之一，比表面积即是1g催化剂或催化剂载体的内（或外）表面积，较大的比表面积可以提高单位质量活性组分的催化效率。载体是负载型催化剂的组成之一，催化活性组分担载在载体表面上，载体主要用于支持活性组分，使催化剂具有特定的物理性状，比如，载体能使制成的催化剂具有合适的形状、尺寸和机械强度，以符合工业反应器的操作要求；又如，载体可使活性组分分散在载体表面上,获得较高的比表面积等等。在应用催化领域中，经常要求催化剂拥有较大的比表面积的同时体积较小，以满足催化剂设置空间的限制和最大限度的发挥催化剂的作用，而较大的比表面积与较小的体积往往不可兼得，这是影响催化剂应用的一个关键因素。
发明内容
本发明要解决的技术问题是在体积一定的情况下，最大化地提高催化剂的比表面积，从而提高催化剂的使用效率。
为了解决上述技术问题，本发明提供了一种催化剂载体，所述载体由多层相似平面体堆砌形成，所述每层相似平面体由多层相似单元框架嵌套形成，所述多层相似单元框架的几何形状与所述每层相似平面体横截面的几何形状相似，所述每层相似单元框架均为弹簧状螺旋结构。
进一步地，所述多层相似平面体之间通过粘接、或利用含有活性组分或助催化作用的金属丝将其钩联、支撑形成网状结构。
进一步地，所述多层相似单元之间通过粘接、或利用含有活性组分或助催化作用的金属丝将其钩联、支撑形成网状结构。
进一步地，所述载体的形状为长方体、柱体、椎体、球体中的一种或几种的组合形式。
进一步地，所述相似平面体的横截面形状为长方形、圆形、三角形、或椭圆形中的一种或几种的组合形式。
进一步地，所述相似单元框架的弹簧状螺旋结构的表面设置为粗糙表面，或者在所述框架表面上设置多个孔洞。
进一步地，所述相似单元框架的弹簧状螺旋结构由活性组分或所述载体上负载的催化剂材料本身制作。
上述技术方案中，利用了将“体”剖成“面”，再将“面”剖成“线”，最后将“线”转换为弹簧状螺旋的材料“放大”过程，保证在不增大催化剂载体体积的情况下，尽可能的增大其比表面积，同时，对弹簧状螺旋框架的表面通过改变粗糙度或者设置孔洞等方式，又进一步地增大载体的比表面积，从而提高催化剂的利用率。
具体实施方式
下面结合附图，进一步详细说明本发明一种催化剂载体的具体实施方式，以下实施例用于说明本发明，但不用来限制本发明的保护范围。
图1a是本发明实施例的长方体状的催化剂载体的结构示意图；
图1b是本发明实施例的长方体状的催化剂载体的多层相似平面体的结构示意图；
图1c是本发明实施例的长方体状的催化剂载体的相似单元框架的结构示意图；
图2a是本发明实施例的椭圆柱状的催化剂载体的结构示意图；
图2b是本发明实施例的椭圆柱状的催化剂载体的多层相似平面体的结构示意图；
图2c是本发明实施例的椭圆柱状的催化剂载体的相似单元框架的结构示意图；
图3是本发明实施例的圆台状的催化剂载体的结构示意图；
图4是本发明实施例的圆球状的催化剂载体的结构示意图；
图5是本发明实施例的圆锥状的催化剂载体的结构示意图；
图6是本发明实施例的圆台状、圆球状和圆锥状的催化剂载体的多层相似平面体的结构示意图；
图7是本发明实施例的圆台状、圆球状和圆锥状的催化剂载体的相似单元框架的结构示意图；
图8是本发明实施例的相似单元框架的弹簧状螺旋结构的圈数与气态污染物的去除率之间的关系图。
参照图1a-1c所示，为本发明实施例的长方体状的催化剂载体及其组成部分的结构示意图。图1a中可以看出，该长方体状的催化剂载体由多层相似的长方体堆砌形成；图1b中可以看出，每层相似的长方体又由多层长方形的相似单元框架嵌套形成，即多层长方形的相似单元框架边长互不相等，逐个嵌套，形成一层所述相似的长方体；图1c中可以看出，每层长方形的相似单元框架为弹簧状螺旋结构；为进一步增大比表面积，该弹簧状螺旋结构的框架表面设置为粗糙表面或设置多个孔洞。
参照图2a-2c所示，为本发明实施例的椭圆柱状的催化剂载体及其组成部分的结构示意图。图2a中可以看出，该椭圆柱状的催化剂载体由多层相似的椭圆柱体堆砌形成；图2b中可以看出，每层相似的椭圆柱体又由多层椭圆形的相似单元框架嵌套形成，即多层椭圆形的相似单元框架的长轴和短轴互不相等，逐个嵌套，形成一层所述相似的椭圆柱体；图2c中可以看出，每层椭圆形的相似单元框架为弹簧状螺旋结构；为进一步增大比表面积，该弹簧状螺旋结构的框架表面设置为粗糙表面或设置多个孔洞。
参照图3-7所示，为本发明实施例的圆台状、圆球状和圆锥状的催化剂载体及其组成部分的结构示意图。图3-5分别示出了圆台状、圆球状和圆锥状的催化剂载体由多层相似的圆台状、圆球状和圆锥状的柱体堆砌形成；图6示出了每层相似的圆台状、圆球状和圆锥状的柱体又由多层圆形的相似单元框架嵌套形成，即多层圆形的相似单元框架半径互不相等，逐个嵌套，形成一层所述相似的圆台状、圆球状和圆锥状的柱体；图7示出了每层圆形的相似单元框架为弹簧状螺旋结构；为进一步增大比表面积，该弹簧状螺旋结构的边框表面设置为粗糙表面或设置多个孔洞。
上述实施例中，所谓的“相似”是指所涉及的几何体或几何图形的形状是相同的，但是具体尺寸不相同，类似于相似三角形、相似多边形等。
上述实施例中，相似单元框架的弹簧状螺旋结构的圈数与气态污染物的去除率之间的关系如图8所示，弹簧状螺旋结构的最佳圈数以实现最高去除率为准来设置。污染物去除率随螺旋圈数的增加呈现先提高后降低的趋势，其最佳圈数由最高污染物去除率所对应的圈数确定，这种先升高后降低的趋势是由于圈数越多，比表面积越大，但穿过其中的空气阻力也随之增强而导致的。当需要将上述催化剂载体用于新装修房屋或污染严重的环境中进行空气污染物净化时，可以采用针对污染物成分的催化剂材料来制作催化剂载体，并且将催化剂载体中弹簧状螺旋结构的圈数设置为最佳圈数，以达到最高污染物去除率。因此，根据不同的环境和目的，采用不同种类的催化剂材料制作催化剂载体，设置不同尺寸和圈数的相似单元框架的弹簧状螺旋结构。
上述各实施例的催化剂载体中，多层相似平面体之间以及多层相似单元框架之间均可以通过粘接、采用含有活性组分，如活性碳纤维或助催化作用的金属丝将其钩联、支撑形成网状结构。
利用图1-7所述的各种几何形状的催化剂载体可以进行空气污染物净化，例如，利用负载二氧化钛催化剂的纳米纤维制作成弹簧状螺旋结构的相似单元，通过上述嵌套、堆砌等方式制作成能去除空气中苯及甲醛的催化剂；又如，将经处理过的贵金属（如铂、铑、钯等）或过渡金属（如铁）制作成弹簧状螺旋结构的相似单元，通过上述嵌套、堆砌等方式制作成能去除空气中氮氧化物的催化剂等。可将上述催化剂安装在空气净化器中以提高空气中相关污染物的净化效果。
吸附剂最常见的活性炭具有微晶结构，微晶排列完全不规则，晶体中有微孔（半径小于20〔埃〕＝10-10米）、过渡孔（半径20~1000）、大孔（半径1000~100000），使它具有很大的内表面，比表面积为500~1700米2/克。
活性炭表面孔穴的多少决定对其对空气污染物的吸附效果，表面积越大，暴露的空穴就越多，吸附效果就越好。因此，使用本发明实施例所提供的催化剂载体，能够更加有效地实现对空气的净化，提高空气净化的速度和净化效率。
工业实用性
本发明所提供的大比表面积、小体积的催化剂载体由多层相似平面体堆砌形成，每层相似平面体又由多层相似单元框架嵌套形成，多层相似单元框架的几何形状与每层相似平面体横截面的几何形状相似，每层相似单元框架均为弹簧状螺旋结构，这样的结构形式是将“体”剖成“面”，再将“面”剖成“线”，最后将“线”转换为螺旋逐级放大过程，以保证在不增大催化剂载体体积的情况下，尽可能的增大其比表面积；同时，在螺旋框架的表面上改变粗糙度或者设置孔洞，又进一步地增大载体的比表面积，从而提高催化剂的利用率，使其对空气污染物净化的效果更佳。

Claims (1)

  1. 1、一种催化剂载体，其特征在于，所述载体由多层相似平面体堆砌形成，所述每层相似平面体由多层相似单元框架嵌套形成，所述多层相似单元框架的几何形状与所述每层相似平面体横截面的几何形状相似，所述每层相似单元框架均为弹簧状螺旋结构。
    2、如权利要求1所述的催化剂载体，其特征在于，所述多层相似平面体之间通过粘接、或利用含有活性组分或助催化作用的金属丝将其钩联、支撑形成网状结构。
    3、如权利要求1所述的催化剂载体，其特征在于，所述多层相似单元框架之间通过粘接、或利用采用含有活性组分或助催化作用的金属丝将其钩联、支撑形成网状结构。
    4、如权利要求1所述的催化剂载体，其特征在于，所述载体的形状为长方体、柱体、椎体、球体中的一种或几种的组合形式。
    5、如权利要求4所述的催化剂载体，其特征在于，所述相似平面体的横截面形状为长方形、圆形、三角形、或椭圆形中的一种或几种的组合形式。
    6、如权利要求1-5中任一项所述的催化剂载体，其特征在于，所述相似单元框架的弹簧状螺旋结构的表面设置为粗糙表面，或者在所述框架表面上设置多个孔洞。
    7、如权利要求6所述的催化剂载体，其特征在于，所述相似单元框架的弹簧状螺旋结构由活性组分或所述载体上负载的催化剂材料本身制作。
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