CN1836777A - Catalyst carbide carrier and its preparation method, regular catalyst and its preparation method - Google Patents

Catalyst carbide carrier and its preparation method, regular catalyst and its preparation method Download PDF

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Publication number
CN1836777A
CN1836777A CN 200610077959 CN200610077959A CN1836777A CN 1836777 A CN1836777 A CN 1836777A CN 200610077959 CN200610077959 CN 200610077959 CN 200610077959 A CN200610077959 A CN 200610077959A CN 1836777 A CN1836777 A CN 1836777A
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Prior art keywords
regular
catalyst
carrier
carbide carrier
supporter
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CN 200610077959
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CN100400160C (en
Inventor
张前程
刘聚明
简丽
马惠言
汪万强
刘全生
牟占军
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Inner Mongolia University of Technology
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Inner Mongolia University of Technology
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Abstract

The present invention discloses regular netted porous carbide carrier suitable for catalyst and its preparation process as well as the regular photocatalyst supported with the carrier and its preparation process. The carbide carrier may be prepared directly on the supporter and has firm adhesion, high mechanical strength and high adsorption performance. The carrier is secondarily supported through coating in easy control of the carrier carbon layer thickness, and the carbonization and activation has specific surface area and pore structure of the carbide carrier capable of being regulated in a wide range, so as to prepare carrier suitable for different catalysts. The carbide carrier supported regular photocatalyst has integrated adsorption and reaction performance, possesses high light flux and low pressure drop, and may be used in the treatment of gaseous and liquid pollutant easily.

Description

Carbide carrier of catalyst and preparation method thereof and regular catalyst and preparation method thereof
Technical field
The present invention relates to carbide carrier of a kind of catalyst and preparation method thereof, especially relate to regular mesh structural porous carbide carrier that a kind of suitable catalyst uses and preparation method thereof, and the regular catalyst that obtains by this carrier loaded photochemical catalyst and preparation method thereof.
Background technology
Catalyst is the core of catalysis technique, and carrier is the important component part of catalyst, and the kind of carrier and character tend to the performance of catalyst is produced a very large impact.
Catalyst carrier has many-sided effect: at first, carrier can improve the decentralization of catalyst activity component, and keeps its stability, makes reaction have higher efficient; Secondly, carrier can be given certain shape of catalyst and size, and makes catalyst have certain mechanical strength, and easy to use and recovery makes it to meet industrial application requirements; In addition, carrier can also improve the adsorptivity of catalyst, or some catalyst is also had promoting catalysis.
Adsorbent class material is to use a class catalyst carrier the most widely.Adsorbent class carrier commonly used has silica gel, active carbon, aluminium oxide, molecular sieve etc.They are the aggregation of powder granule normally, in actual applications, has often needed with load the carrier granular immobilization again of catalyst, so that reduce the phase resistance that flows, improve reaction efficiency, be beneficial to the recycling of catalyst simultaneously, avoid the waste of catalyst and reactant is polluted.
On the other hand, in the photocatalysis technology field, especially be used for aspect the pollution control in photocatalysis, the load technology of catalyst is an important problem always.Because pollutant levels to be processed are very low generally speaking,, will create certain condition and make reactant molecule can be adsorbed on the surface of catalyst effectively so want that higher catalytic degradation efficient is arranged.Common way is that the adsorbing agent carrier particle is fixed on the supporter with the bonding method of adhesive, and then with catalyst cupport on adsorbing agent carrier, suction-operated by adsorbent with reactant absorption, be enriched to around the photochemical catalyst, increase the concentration of local reaction thing, to improve reaction rate and to avoid the intermediate product volatilization to cause secondary pollution.
But this fixed form exist such as the long-pending loss of: adsorbent surface too much, activity of such catalysts and surface area reduce carrier granular that excessive and the not enough and long-term UV-irradiation of the firmness that is adhesively fixed causes adhesive to decompose to be caused from problems such as supporter come off, hindered the exploitation of practicability, industrialization and the extensive photocatalytic system of photocatalysis technology.
Summary of the invention
The object of the present invention is to provide a kind of regular mesh structural porous carbide carrier of catalyst, this kind catalyst carrier directly prepares on supporter, and good mechanical strength and absorption property are arranged, and has fundamentally avoided carrier from problems such as supporter come off.
Another object of the present invention is to provide a kind of preparation method of regular mesh structural porous carbide carrier of catalyst.
A further object of the present invention is to provide a kind of carbide carrier support type regular catalyst, this photochemical catalyst integrates adsorptivity and reactivity, have high adsorption, high light flux and low pressure degradation characteristic, can be advantageously used in gas phase or the liquid phase light-catalyzed reaction system.
The 4th purpose of the present invention is to provide a kind of preparation method of carbide carrier support type regular catalyst.
First purpose of the present invention is implemented by following technical scheme: a kind of carbide carrier of catalyst, and the preparation predecessor of carrier is selected resinae or bitumen for use, and supporter selects high temperature resistant temperature greater than 1000 ℃ mesh material; Described predecessor evenly is coated on the described supporter, and applied thickness is as the criterion not stop up mesh; The described predecessor of evenly coating is directly prepared the regular mesh structural porous carbide carrier on supporter through curing process, charring process, activating process successively, the pore-size distribution of described regular carbide carrier is based on mesopore, porosity is more than or equal to 50% in the described pore-size distribution, and described mesopore pore size distribution range is 2~50nm.
The material of described network structure supporter is metal material or nonmetallic materials, and described metal is: copper, iron or stainless steel; Nonmetallic materials are cordierite ceramics, quartz glass or charcoal.
The space structure of described network structure supporter is plane network structure or space network; Described plane network structure is a triangle, or polygon, or circular, or irregular abnormity; Described space network is a chevron-shaped, or conical, or cylindrical, or pyramid, or prismatic, or truncated cone-shaped, or terrace with edge shape.
Described resinae predecessor is novolac resin, thermosetting phenolic resin, any of amino resins, epoxy resin or unsaturated polyester resin or several mixture; Described pitch class predecessor is any one or two kinds of mixture of asphalt and tar asphalt.Described novolac resin need add curing agent in use, and curing agent is a hexamethylenetetramine.
Second purpose of the present invention implemented by following technical scheme: a kind of preparation method of carbide carrier of catalyst includes:
(1), at first selecting high temperature resistant temperature is supporter greater than 1000 ℃ mesh material, described supporter is cleaned dry for standby;
(2), described predecessor selects the resinae material for use, regulates resin viscosity, till can being coated to resin on the supporter easily; Or described predecessor selects bitumen for use, with described bitumen heat fused;
(3), described predecessor that (2) are prepared evenly is coated on the described supporter of dry for standby, do not stop up mesh during coating;
(4), curing process: the described supporter that will apply described resinae predecessor is put in the baking oven, evenly is warming up to 90~180 ℃, and constant temperature 1~8h, and described resinae predecessor is solidificated on the described supporter; Or, in air atmosphere, being heated to 300~500 ℃ with the pitch class predecessor that described coating finishes, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the described supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) described step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh.
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~(500~900 ℃) 1~30 ℃/min;
(500~900 ℃) constant temperature 1~8h;
(500~900℃)~(600~1000℃) 1~30℃/min;
(600~1000 ℃) constant temperature 1~8h, and when beginning constant temperature, feed alive
Gasification when constant temperature finishes, stops to feed activation gas;
1~30 ℃/min of (500~900 ℃)~room temperature
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more dry, promptly obtain mesh structural porous carbide carrier.
Described activation gas is any of steam, air and carbon dioxide, and the feeding amount of activation gas is 1~1000ml/min;
The 3rd purpose of the present invention implemented by following technical scheme: carbide carrier support type regular catalyst by load have a mesh structural porous as mentioned above carbide carrier of photocatalytic activity material, be combined into a regular integral body, thereby obtain carbide carrier support type regular catalyst;
Described carbide carrier support type regular catalyst, by at least one load have a photocatalytic activity material, described plane netted porous charcoal thing carrier or described solid netted porous carbide carrier, the regular integral body of composition.
Described carbide carrier support type regular catalyst, be to be parallel to each other successively by at least one plane quadrilateral regular catalyst and quadrangle chevron-shaped regular catalyst to stack, between every adjacent two layers plane quadrilateral regular catalyst, do supporter with the described chevron-shaped regular catalyst of one deck, the vertical plane of wherein said quadrangle chevron-shaped regular catalyst is identical with the vertical plane size of described plane quadrilateral regular catalyst, the shape unanimity; The shortest limit of described plane quadrilateral regular catalyst is 10~20: 1 with the ratio of the spacing of adjacent two layers plane quadrilateral regular catalyst, and contact point is fixed and formed a regular integral body between adjacent layer.
Described carbide carrier support type regular catalyst, the triangle identical by at least one shape, that size is identical, or polygon, or it is circular, or the netted regular catalyst in the plane of irregular abnormity, the placement that is parallel to each other successively of different plane, and average every meter catalyst amounts that comprises is 1~30, fixed by shell and forms a regular integral body.
Described carbide carrier support type regular catalyst, the taper shape identical by at least one shape, that size is identical, or pyramid, or truncated cone-shaped, or the solid netted regular catalyst of terrace with edge shape, along the coaxial line placement that is parallel to each other successively, average every meter conial vertex number that comprises is 1~30, is fixed by shell and forms a regular integral body; Described truncated cone-shaped or the solid netted regular catalyst of terrace with edge shape, its upper bottom surface and bottom surface also are the regular catalyst of porous network structure.
Described carbide carrier support type regular catalyst, highly identical by at least one, it is described cylindrical that diameter does not wait, or prismatic solid netted regular catalyst, fix and form a regular integral body by the ascending order of diameter suit successively, its adjacent parallel interplanar distance greater than zero less than outermost layer cylinder or prismatic diameter.
Described material with photocatalytic activity is any one or two kinds of above mixtures of titanium dioxide, tungstic acid, antimony oxide, zirconium dioxide, magnesia, zinc oxide.
The 4th purpose of the present invention is to provide the preparation method of regular catalyst, includes:
(1), at first selecting high temperature resistant temperature is supporter greater than 1000 ℃ mesh material, described supporter is cleaned dry for standby;
(2), described predecessor selects the resinae material for use, regulates resin viscosity, till can being coated to resin on the supporter easily; Or described predecessor selects bitumen for use, with described bitumen heat fused;
(3), described predecessor that (2) are prepared evenly is coated on the described supporter of dry for standby, do not stop up mesh during coating;
(4), curing process: the described supporter that will apply described resinae predecessor is put in the baking oven, evenly to be warming up to 90~180 ℃ less than the heating rate of 10 ℃/min greater than 0 ℃/min, and constant temperature 1~8h, described resinae predecessor is solidificated on the described supporter; Or, in air atmosphere, being heated to 300~500 ℃ with the pitch class predecessor that described coating finishes, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the described supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) described step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh.
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~(500~900 ℃) 1~30 ℃/min;
(500~900 ℃) constant temperature 1~8h;
(500~900℃)~(600~1000℃) 1~30℃/min;
(600~1000 ℃) constant temperature 1~8h, and when beginning constant temperature, feed alive
Gasification when constant temperature finishes, stops to feed activation gas;
1~30 ℃/min of (500~900 ℃)~room temperature
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more dry, promptly obtain mesh structural porous carbide carrier.
(8), described material with photocatalytic activity is become uniform suspension with the deionized water sonic oscillation, and add percentage by weight be 2%~3% KP1 as bonding agent, then this suspension evenly is coated on (7) resulting mesh structural porous carbide carrier; With load have the mesh structural porous carbide carrier of the material of photocatalytic activity, at 100~300 ℃ of freeze-day with constant temperature 2~3h, promptly obtain the single regular catalyst of plane network structure or space network.
The preparation method of regular catalyst also includes following step: by at least one load have a photocatalytic activity material, described plane netted porous charcoal thing carrier or described solid netted porous carbide carrier, a single regular integral body of composition;
Or by at least one load have a mesh structural porous carbide carrier of quadrangular plan of photocatalytic activity material, be parallel to each other successively with the solid netted porous carbide carrier of quadrangle chevron-shaped and stack, between the netted porous charcoal thing carrier of the described plane of every adjacent two layers, do supporter with the solid netted porous carbide carrier of the described quadrangle chevron-shaped of one deck, the vertical plane of the solid netted porous carbide carrier of wherein said quadrangle chevron-shaped is identical with the vertical plane size of the mesh structural porous carbide carrier of described quadrangular plan, the shape unanimity; The shortest limit of described plane netted porous charcoal thing carrier is 10~20: 1 with the ratio of the described plane of adjacent two layers netted porous charcoal thing carrier distance, and contact point is fixed and formed a regular integral body between adjacent layer;
Or by at least one load have an identical shaped described triangle of photocatalytic activity material, polygon, circular, or the plane of irregular abnormity netted porous charcoal thing carrier, the placement that is parallel to each other successively of different plane, average every meter quantity that comprises catalyst is 1~30, is fixed by shell and forms a regular integral body;
Or by at least one load have an identical shaped described taper shape of photocatalytic activity material, or pyramid or truncated cone-shaped, or the solid netted porous carbide carrier of terrace with edge shape, along the placement that is parallel to each other successively of coaxial line direction, average every meter conial vertex number that comprises is 1~30, is fixed by shell and forms a regular integral body; The solid netted porous carbide carrier of described truncated cone-shaped or terrace with edge shape, its upper bottom surface and bottom surface also are porous network structure;
Or by at least one load have the described cylindrical of photocatalytic activity material, prismatic solid netted porous carbide carrier, choose highly identical, the described load that diameter does not wait have the cylindrical of photocatalytic activity material, prismatic solid netted porous carbide carrier, fix and form a regular integral body by the ascending order of diameter suit successively, its adjacent parallel interplanar distance greater than zero less than outermost layer cylinder or prismatic diameter.
The invention has the advantages that: the carbide carrier of this catalyst is mesh structural porous carbide carrier, can directly prepare on supporter, and bonding firmly have very high mechanical strength and absorption property, fundamentally avoided carrier from problems such as supporter come off.Its preparation method novelty, simple.
Support shapes can change with the variation of supporter shape in addition, simultaneously because the existence of supporter also makes carrier have mechanical strength preferably.Adopt the mode of coating to carry out the secondary load of carrier, make the thickness of carrier charcoal layer control easily, by charing and activation, make the surface area and the pore structure of carbide carrier in a very wide scope, to regulate and control, be convenient to make the carrier that is fit to different catalysts, to adapt to different actual conditions.
Carbide carrier support type regular catalyst is to integrate adsorptivity and reactive photochemical catalyst, has the characteristic of high light flux, low pressure drop, can be used for the pollution control of gas phase or liquid phase easily.Its preparation method is simple, novel.
Description of drawings:
Fig. 1 is the netted single regular catalyst of embodiment 1 rectangular planes.
Fig. 2 is the solid netted single regular catalyst of embodiment 1 rectangle chevron-shaped.
Fig. 3 is the structural representation of embodiment 1 solid netted regular catalyst.
Fig. 4 is the structural representation of embodiment 2 conical regular network diaphragm catalyst.
Fig. 5 is the structural representation of embodiment 3 circular netted regular catalysts.
The specific embodiment:
Embodiment 1
Embodiment 1.1: a kind of carbide carrier of catalyst, the preparation predecessor of carrier is selected novolac resin for use, curing agent is six methines, four ammoniums, and supporter selects high temperature resistant temperature greater than the netted and 8 solid netted order ferrous metal silk screens of rectangle chevron-shaped of 1000 ℃ rectangular planes.In novolac resin, mix mass percent and be 15% curing agent hexamethylenetetramine, mix.This resin evenly is coated on the ferrous metal silk screen, and applied thickness is as the criterion not stop up mesh.The product of evenly coating is directly prepared the regular mesh structural porous carbide carrier on the ferrous metal silk screen through curing process, charring process, activating process successively, and the middle porosity of regular carbide carrier is 12%.Wherein predecessor also can be a thermosetting phenolic resin, and any of amino resins, epoxy resin or unsaturated polyester resin also can be thermosetting phenolic resin, several mixtures of amino resins, epoxy resin or unsaturated polyester resin.
Embodiment 1.2: the preparation method of the carbide carrier of the catalyst of embodiment 1.1 includes:
(1), at first select the ferrous metal silk screen that high temperature resistant temperature is netted greater than 1000 ℃ rectangular planes and the rectangle chevron-shaped is solid netted, woven wire is cleaned dry for standby;
(2), select novolac resin for use, mix mass percent and be 15% curing agent hexamethylenetetramine, regulate viscosity with acetone, can be coated on the woven wire easily up to the novolac resin that mixes curing agent and get final product;
(3), novolac resin that (2) are prepared evenly is coated on the woven wire of dry for standby, do not stop up mesh during coating;
(4), curing process: the woven wire that will apply novolac resin is put in the baking oven, evenly is warming up to 90 ℃, and constant temperature 1h, and novolac resin is solidificated on the ferrous metal silk screen;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh.
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~500 2 ℃/min;
500 ℃ of constant temperature 2h;
500~600℃ 8℃/min;
600 ℃ of constant temperature 2h, and when beginning constant temperature, feed activation
Gas when constant temperature finishes, stops to feed activation gas;
2 ℃/min of 600 ℃~room temperature
Activation gas is steam in the above-mentioned steps, and the feeding flow is 20ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
Embodiment 1.3: utilize embodiment 1.1 and embodiment 1.2 resulting mesh structural porous carbide carriers to prepare regular catalyst, be will have a photocatalytic activity titanium dichloride load in aforesaid rectangular planes on the netted or solid netted porous carbide carrier of rectangle chevron-shaped, be combined into a regular integral body respectively, and obtain single regular network diaphragm catalyst: as Fig. 1, one is the netted single regular catalyst of rectangular planes, as Fig. 2, another is the solid netted single regular catalyst of rectangle chevron-shaped.The material that wherein has photocatalytic activity also can be any one or two kinds of above mixtures of tungstic acid, antimony oxide, zirconium dioxide, magnesia, zinc oxide.
Embodiment 1.4: as shown in Figure 3, the single regular catalyst that utilizes embodiment 1.3 to obtain, be parallel to each other successively by seven netted regular catalysts of rectangular planes and six solid netted regular catalysts of rectangle chevron-shaped and stack, between the netted regular catalyst of every adjacent two layers rectangular planes, do supporter with the solid netted regular catalyst of one deck rectangle chevron-shaped, the vertical plane of the solid netted regular catalyst of rectangle chevron-shaped is identical with the vertical plane size of the netted regular catalyst of rectangular planes, the shape unanimity; The shortest limit of the netted regular catalyst of described rectangular planes can be 10: 1 with the ratio of the spacing of the netted regular catalyst of adjacent two layers rectangular planes, or 15: 1, or 20: 1 etc., contact point is fixed and is formed a regular integral body between adjacent layer.
Embodiment 1.5: the preparation method of the regular catalyst of embodiment 1.3 includes:
(1), at first select the ferrous metal silk screen that high temperature resistant temperature is netted greater than 1000 ℃ rectangular planes and the rectangle chevron-shaped is solid netted, woven wire is cleaned dry for standby;
(2), select novolac resin for use, mix mass percent and be 15% curing agent hexamethylenetetramine, regulate viscosity with acetone, can be coated on the woven wire easily up to the novolac resin that mixes curing agent and get final product;
(3), novolac resin that (2) are prepared evenly is coated on the woven wire of dry for standby, do not stop up mesh during coating;
(4), curing process: the woven wire that will apply novolac resin is put in the baking oven, evenly is warming up to 90 ℃, and constant temperature 1h, and novolac resin is solidificated on the ferrous metal silk screen;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh.
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~500 2 ℃/min;
500 ℃ of constant temperature 2h;
500~600℃ 8℃/min;
600 ℃ of constant temperature 2h, and when beginning constant temperature, feed activation
Gas when constant temperature finishes, stops to feed activation gas;
2 ℃/min of 600 ℃~room temperature
Activation gas is steam in the above-mentioned steps, and the feeding flow is 20ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
(8), titanium dioxide is become uniform suspension with the deionized water sonic oscillation, and the percentage by weight that adds suspension be 2%~3% KP1 as bonding agent, then this suspension evenly is coated on (7) resulting mesh structural porous carbide carrier; There is the mesh structural porous carbide carrier of titanium dioxide to put into the electric furnace of temperature programming function load, at 100~300 ℃ of freeze-day with constant temperature 2~3h, promptly obtain the single regular catalyst of single plane network structure or space network, become 1.3 described regular catalysts as embodiment.
Shown in figure three, be parallel to each other successively by seven netted regular catalysts of rectangular planes and six solid netted regular catalysts of rectangle chevron-shaped and stack, between the netted regular catalyst of every adjacent two layers rectangular planes, do supporter with the solid netted regular catalyst of one deck rectangle chevron-shaped, the vertical plane of the solid netted regular catalyst of rectangle chevron-shaped is identical with the vertical plane size of the netted regular catalyst of rectangular planes, the shape unanimity; The shortest limit of the netted regular catalyst of described rectangular planes can be 10: 1 with the ratio of the spacing of the netted regular catalyst of adjacent two layers rectangular planes, or 15: 1, or 20: 1 etc., contact point is fixed and is formed a regular integral body between adjacent layer, becomes the 1.4 described regular catalysts as embodiment.
Wherein the woven wire of the foregoing description also can be selected copper or stainless steel metal silk screen for use, the shape of final regular catalyst is to be determined by the shape of single regular catalyst and combined situation, and the shape of single regular catalyst is by the shape decision as the woven wire of supporter; Wherein the shape of woven wire can be square or rhombus, or trapezoidal, or irregular quadrangle.
The activation gas of present embodiment 1 also can be any of carbon dioxide and air.
Present embodiment 1 used predecessor also can be thermosetting phenolic resin, any of amino resins, epoxy resin or unsaturated polyester resin or several mixture
The supporter of present embodiment 1 also can be copper woven wire, stainless steel metal silk screen, or the cordierite ceramic net, or the carbonaceous Web materials.
The material with photocatalytic activity of present embodiment 1 also can be any one or two kinds of above mixtures of tungstic acid, antimony oxide, zirconium dioxide, magnesia, zinc oxide.
Embodiment 2:
Embodiment 2.1: a kind of carbide carrier of catalyst, and the preparation predecessor of carrier is selected thermosetting phenolic resin for use, and supporter selects high temperature resistant temperature greater than 1000 ℃ conical 8 order stainless steel cloths.The above-mentioned predecessor of choosing evenly is coated on the silk screen of above-mentioned material, and applied thickness is as the criterion not stop up mesh.The product of evenly coating is directly prepared at the online regular mesh structural porous carbide carrier of conical stainless steel metal wire through curing process, charring process, activating process successively, and the middle porosity of regular carbide carrier is 20%.
Embodiment 2.2: the preparation method of the carbide carrier of the catalyst of embodiment 2.1 includes:
(1), at first select high temperature resistant temperature greater than 1000 ℃ conical stainless steel cloth, silk screen is cleaned dry for standby;
(2), select thermosetting phenolic resin for use, with the thermosetting phenolic resin of choosing, regulate viscosity with acetone, can conveniently be coated on the silk screen up to thermosetting phenolic resin and get final product;
(3), thermosetting phenolic resin that (2) are prepared evenly is coated on the woven wire of dry for standby, do not stop up mesh during coating;
(4), curing process: the stainless steel cloth that will apply thermosetting phenolic resin is put in the baking oven, evenly is warming up to 180 ℃, and constant temperature 8h, and it is online to make thermosetting phenolic resin be solidificated in stainless steel metal wire;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~700 10 ℃/min;
700 ℃ of constant temperature 4h;
700~800℃ 20℃/min;
800 ℃ of constant temperature 1h, and when beginning constant temperature, feed activation gas,
When constant temperature finishes, stop to feed activation gas;
10 ℃/min of 800 ℃~room temperature
Activation gas is air in the above-mentioned steps, and the feeding flow is 1000ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
Embodiment 2.3: utilize embodiment 2.1 and embodiment 2.2 resulting mesh structural porous carbide carriers to prepare regular catalyst, be the zirconia-supported that will have a photocatalytic activity on conical solid netted porous carbide carrier as mentioned above, and obtain single conical regular network diaphragm catalyst.
Embodiment 2.4: as shown in Figure 4, utilize embodiment 2.3 resulting single regular catalysts: three solid netted regular catalysts of taper shape, along the parallel placement of coaxial line direction, average every meter conial vertex number that comprises can be 5, or 15, or 20, fixed by shell and to be formed a regular integral body, become regular catalyst;
Embodiment 2.5: the preparation method of the regular catalyst that embodiment 2.3 is single includes:
(1), at first select high temperature resistant temperature greater than 1000 ℃ conical stainless steel cloth, silk screen is cleaned dry for standby;
(2), select thermosetting phenolic resin for use, with the thermosetting phenolic resin of choosing, regulate viscosity with acetone, can conveniently be coated on the silk screen up to thermosetting phenolic resin and get final product;
(3), thermosetting phenolic resin that (2) are prepared evenly is coated on the woven wire of dry for standby, do not stop up mesh during coating;
(4), curing process: the stainless steel cloth that will apply thermosetting phenolic resin is put in the baking oven, evenly is warming up to 180 ℃, and constant temperature 8h, and it is online to make thermosetting phenolic resin be solidificated in stainless steel metal wire;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~700 10 ℃/min;
700 ℃ of constant temperature 4h;
700~800℃ 20℃/min;
800 ℃ of constant temperature 1h, and when beginning constant temperature, feed activation
Gas when constant temperature finishes, stops to feed activation gas;
10 ℃/min of 800 ℃~room temperature
Activation gas is air in the above-mentioned steps, and the feeding flow is 1000ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
(8), the zirconium dioxide that will have a photocatalytic activity becomes uniform suspension with the deionized water sonic oscillation, and add weight be 2%~3% KP1 as bonding agent, then this suspension evenly is coated on (7) resulting mesh structural porous carbide carrier; There is the mesh structural porous carbide carrier of zirconium dioxide to put into the electric furnace of temperature programming function load, at 100~300 ℃ of freeze-day with constant temperature 2~3h, promptly obtain the regular catalyst of single conical space network, become 2.3 described regular catalysts as embodiment.
As shown in Figure 5, with three solid netted regular catalysts of taper shape, along the parallel placement of coaxial line direction, average every meter conial vertex number that comprises can be 5, or 15, or 20, fixed by shell and to be formed a regular integral body, become 2.4 described regular catalysts as embodiment.
Wherein the support body material of the foregoing description also can be cordierite ceramic, the network structure of quartz glass or charcoal.The shape of final regular catalyst is to be determined by the shape of single regular catalyst and combined situation, and the shape of single regular catalyst is by the shape decision as the woven wire of supporter; Wherein the shape of supporter can be pyramid, or truncated cone-shaped, or terrace with edge shape, and truncated cone-shaped or the solid netted supporter of terrace with edge shape, its upper bottom surface and bottom surface also are porous network structure.
Another kind of regular catalyst is to choose that at least one is highly identical, it is cylindrical that diameter does not wait, or prismatic supporter, finally obtain regular catalyst as shown in Figure 6 by the foregoing description, this regular catalyst is fixed by the ascending order of diameter suit successively and is formed a regular integral body, its adjacent parallel interplanar distance greater than zero less than outermost layer cylinder or prismatic diameter.
The material with photocatalytic activity of present embodiment 2 also can be any one or two kinds of above mixtures of magnesia, zinc oxide.
The activation gas of present embodiment 2 also can be any of carbon dioxide and steam.
Present embodiment 2 used predecessors also can be for adding the novolac resin of curing agent, any of amino resins, epoxy resin or unsaturated polyester resin or several mixture
The material with photocatalytic activity of present embodiment 2 also can be any one or two kinds of above mixtures of titanium dioxide, tungstic acid, antimony oxide, magnesia, zinc oxide.
Embodiment 3:
Embodiment 3.1: a kind of carbide carrier of catalyst, and the preparation predecessor of carrier is selected asphalt for use, and supporter selects high temperature resistant temperature greater than 1000 ℃ circular cordierite ceramic net; Wherein, the mesh diameter of a beautiful gem green stone net is about 6~8mm.It is online evenly to be coated in cordierite ceramic after the asphalt fusion, and applied thickness is as the criterion not stop up mesh.Successively through peroxidating melting process not, charring process, activating process are directly prepared at the online regular mesh structural porous carbide carrier of cordierite ceramic with the asphalt of evenly coating, and the middle porosity of this regular carbide carrier is 40%.
Embodiment 3.2: the preparation method of the carbide carrier of the catalyst of embodiment 3.1 includes:
(1), at first select high temperature resistant temperature greater than 1000 ℃ circular cordierite ceramic net, circular cordierite ceramic net is cleaned dry for standby;
(2), select asphalt for use, with the asphalt heating and melting;
(3), it is online that the asphalt that (2) are prepared evenly is coated in the cordierite ceramic of dry for standby;
(4), oxidation melting process not: will apply good asphalt predecessor, and put into the electric furnace of temperature programming function, and be heated to 300~500 ℃ under the air atmosphere, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~800 20 ℃/min;
800 ℃ of constant temperature 8h;
800~900℃ 30℃/min;
900 ℃ of constant temperature 5h, and when beginning constant temperature, feed activation gas,
When constant temperature finishes, stop to feed activation gas;
20 ℃/min of 600 ℃~room temperature
Activation gas is carbon dioxide in the above-mentioned steps, and the feeding flow is 500ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
Embodiment 3.3: utilize embodiment 3.1 and embodiment 3.2 resulting mesh structural porous carbide carriers to prepare regular catalyst, be that the material antimony oxide that will have a photocatalytic activity loads on as mentioned above on the carbide carrier, and obtain single circular netted regular catalyst;
Embodiment 3.4: as shown in Figure 5, utilize embodiment 3.3 resulting single regular catalysts: three netted single regular catalysts of circular flat, the parallel placement of axis direction along the vertical center of circle, average every meter quantity that comprises catalyst is 1~30, fixed the regular integral body of composition by shell, become regular whole photochemical catalyst.
Embodiment 3.5: the preparation method of the regular catalyst that embodiment 3.3 is single includes:
(1), at first select high temperature resistant temperature greater than 1000 ℃ circular cordierite ceramic net, circular cordierite ceramic net is cleaned dry for standby;
(2), select asphalt for use, with the asphalt heating and melting;
(3), it is online that the asphalt that (2) are prepared evenly is coated in the cordierite ceramic of dry for standby;
(4), oxidation melting process not: will apply good asphalt predecessor, and put into the electric furnace of temperature programming function, and be heated to 300~500 ℃ under the air atmosphere, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh;
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~800 20 ℃/min;
800 ℃ of constant temperature 8h;
800~900℃ 30℃/min;
900 ℃ of constant temperature 5h, and when beginning constant temperature, feed activation
Gas when constant temperature finishes, stops to feed activation gas;
20 ℃/min of 600 ℃~room temperature
Activation gas is carbon dioxide in the above-mentioned steps, and the feeding flow is 500ml/min.
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more, and 105 ℃ of oven dry 2h promptly obtain mesh structural porous carbide carrier.
(8), the material antimony oxide that will have a photocatalytic activity becomes uniform suspension with the deionized water sonic oscillation, and the KP1 that adds 2%~3% (weight) evenly is coated in this suspension on (7) resulting mesh structural porous carbide carrier as bonding agent then; There is the mesh structural porous carbide carrier of antimony oxide to put into the electric furnace of temperature programming function load, at 100~300 ℃ of freeze-day with constant temperature 2~3h, promptly obtain the cancellated regular catalyst of single circular flat, become 3.3 described regular catalysts as embodiment.
As shown in Figure 8, with the cancellated photochemical catalyst of described single plane, the parallel placement of axis direction along the vertical center of circle, every meter quantity that comprises catalyst is 20 slices/meter, 10 slices/meter, 30 slices/meter, fixed by shell and to be formed a regular integral body, become 3.4 described regular catalysts as embodiment.
Present embodiment 3 used predecessors also can be tar asphalt.
The supporter of present embodiment 3 also can be the stainless steel metal wire net, or the carbonaceous Web materials.
The space structure of the supporter of present embodiment 3 also can be triangle, polygon, ellipse.
The activation gas of present embodiment 3 also can be any of air and steam.
The material with photocatalytic activity of present embodiment 2 also can be any one or two kinds of above mixtures of titanium dioxide, tungstic acid, zirconium dioxide, magnesia, zinc oxide.

Claims (17)

1, a kind of carbide carrier of catalyst is characterized in that, the preparation predecessor of carrier is selected resinae or bitumen for use, and supporter selects high temperature resistant temperature greater than 1000 ℃ mesh material; Described predecessor evenly is coated on the described supporter, and applied thickness is as the criterion not stop up mesh; The described predecessor of evenly coating is directly prepared the regular mesh structural porous carbide carrier on supporter through curing process, charring process, activating process successively, and the pore-size distribution of described regular carbide carrier is based on mesopore.
2, the carbide carrier of a kind of catalyst as claimed in claim 1 is characterized in that, the material of described network structure supporter is metal or nonmetallic materials, and described metal is: copper, iron or stainless steel; Nonmetallic materials are cordierite ceramic, quartz glass or charcoal.
3, the carbide carrier of a kind of catalyst as claimed in claim 1 is characterized in that, the space structure of described network structure supporter is plane network structure or space network; Described plane network structure is a triangle, polygon, circle, or irregular abnormity; Described space network is a chevron-shaped, or conical, or cylindrical, or pyramid, or prismatic, or truncated cone-shaped, or terrace with edge shape.
4, the carbide carrier of a kind of catalyst as claimed in claim 1, it is characterized in that, described resinae predecessor is novolac resin, thermosetting phenolic resin, any of amino resins, epoxy resin or unsaturated polyester resin or several mixture; Described pitch class predecessor is any one or two kinds of mixture of asphalt or tar asphalt.
5, the carbide carrier of a kind of catalyst as claimed in claim 4 is characterized in that, described novolac resin need add curing agent in use, and curing agent is a hexamethylenetetramine.
6, the carbide carrier of a kind of catalyst as claimed in claim 1 is characterized in that, porosity is more than or equal to 50% in the described pore-size distribution, and described mesopore pore size distribution range is 2~50nm.
7, a kind of preparation method of carbide carrier of catalyst is characterized in that, this preparation method includes:
(1), at first selecting high temperature resistant temperature is supporter greater than 1000 ℃ mesh material, described supporter is cleaned dry for standby;
(2), described predecessor selects the resinae material for use, regulates resin viscosity, till can being coated to resin on the supporter easily; Or described predecessor selects bitumen for use, with described bitumen heat fused;
(3), described predecessor that (2) are prepared evenly is coated on the described supporter of dry for standby, do not stop up mesh during coating;
(4), curing process: the described supporter that will apply described resinae predecessor is put in the baking oven, evenly is warming up to 90~180 ℃, and constant temperature 1~8h, and described resinae predecessor is solidificated on the described supporter; Or, in air atmosphere, being heated to 300~500 ℃ with the pitch class predecessor that described coating finishes, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the described supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) described step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh;
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~(500~900 ℃) 1~30 ℃/min;
(500~900 ℃) constant temperature 1~8h;
(500~900℃)~(600~1000℃) 1~30℃/min;
(600~1000 ℃) constant temperature 1~8h, and logical when beginning constant temperature
Go into to activate gas, when constant temperature finishes, stop to lead to
Go into to activate gas;
1~30 ℃/min of (500~900 ℃)~room temperature
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more dry, promptly obtain mesh structural porous carbide carrier.
8, the preparation method of the carbide carrier of a kind of catalyst as claimed in claim 7 is characterized in that: described activation gas is any of steam, air and carbon dioxide, and the feeding amount of activation gas is 1~1000ml/min;
9, carbide carrier support type regular catalyst, it is characterized in that: by load have the photocatalytic activity material as the arbitrary described mesh structural porous carbide carrier of claim 1~6, be combined into a regular integral body, and obtain carbide carrier support type regular catalyst;
10, regular catalyst as claimed in claim 9, it is characterized in that, described carbide carrier support type regular catalyst, by at least one load have a photocatalytic activity material, described plane netted porous charcoal thing carrier or described solid netted porous carbide carrier, the regular integral body of composition.
11, regular catalyst as claimed in claim 9, it is characterized in that, described carbide carrier support type regular catalyst, be to be parallel to each other successively by at least one plane quadrilateral regular catalyst and quadrangle chevron-shaped regular catalyst to stack, between every adjacent two layers plane quadrilateral regular catalyst, do supporter with the described chevron-shaped regular catalyst of one deck, the vertical plane of wherein said quadrangle chevron-shaped regular catalyst is identical with the vertical plane size of described plane quadrilateral regular catalyst, the shape unanimity; The shortest limit of described plane quadrilateral regular catalyst is 10~20: 1 with the ratio of the spacing of adjacent two layers plane quadrilateral regular catalyst, and contact point is fixed and formed a regular integral body between adjacent layer.
12, regular catalyst as claimed in claim 9, it is characterized in that, described carbide carrier support type regular catalyst, the triangle identical by at least one shape, that size is identical, or polygon, or circular, or the netted regular catalyst in the plane of irregular abnormity, the placement that is parallel to each other successively of different plane, and average every meter catalyst amounts that comprises is 1~30, fixed by shell and forms a regular integral body.
13, regular catalyst as claimed in claim 9, it is characterized in that, described carbide carrier support type regular catalyst, the taper shape identical by at least one shape, that size is identical, or pyramid, or truncated cone-shaped, or the solid netted regular catalyst of terrace with edge shape, along the coaxial line placement that is parallel to each other successively, average every meter conial vertex number that comprises is 1~30, is fixed by shell and forms a regular integral body; Described truncated cone-shaped or the solid netted regular catalyst of terrace with edge shape, its upper bottom surface and bottom surface also are the regular catalyst of porous network structure.
14, regular catalyst as claimed in claim 9, it is characterized in that, described carbide carrier support type regular catalyst, highly identical by at least one, it is described cylindrical that diameter does not wait, or prismatic solid netted regular catalyst, fix and form a regular integral body by the ascending order of diameter suit successively, its adjacent parallel interplanar distance greater than zero less than outermost layer cylinder or prismatic diameter.
15, regular catalyst as claimed in claim 9 is characterized in that, described material with photocatalytic activity is any one or two kinds of above mixtures of titanium dioxide, tungstic acid, antimony oxide, zirconium dioxide, magnesia, zinc oxide.
16, the preparation method of regular catalyst is characterized in that, its preparation method includes:
(1), at first selecting high temperature resistant temperature is supporter greater than 1000 ℃ mesh material, described supporter is cleaned dry for standby;
(2), described predecessor selects the resinae material for use, regulates resin viscosity, till can being coated to resin on the supporter easily; Or described predecessor selects bitumen for use, with described bitumen heat fused;
(3), described predecessor that (2) are prepared evenly is coated on the described supporter of dry for standby, do not stop up mesh during coating;
(4), curing process: the described supporter that will apply described resinae predecessor is put in the baking oven, evenly to be warming up to 90~180 ℃ less than the heating rate of 10 ℃/min greater than 0 ℃/min, and constant temperature 1~8h, described resinae predecessor is solidificated on the described supporter; Or, in air atmosphere, being heated to 300~500 ℃ with the pitch class predecessor that described coating finishes, constant temperature 1~14h makes it form oxidation and does not melt pitch prill, is solidificated on the described supporter;
(5), the product after will solidifying takes out, and is cooled to room temperature, can apply repeatedly, solidify by (3), (4) described step, to increase the thickness of overlay, the maximum ga(u)ge of overlay is as the criterion not stop up mesh.
(6), the product that will dispose through above-mentioned steps; put into airtight container; container is placed in the electric furnace of temperature programming function; under the nitrogen protection condition; carry out temperature programming and feed the operation of activation gas by following step, promptly the described product that is cured is carried out charing, activation processing:
Feed the air in the nitrogen replacement container in advance
Room temperature~(500~900 ℃) 1~30 ℃/min;
(500~900 ℃) constant temperature 1~8h;
(500~900℃)~(600~i000℃) 1~30℃/min;
(600~1000 ℃) constant temperature 1~8h, and logical when beginning constant temperature
Go into to activate gas, when constant temperature finishes, stop to lead to
Go into to activate gas;
1~30 ℃/min of (500~900 ℃)~room temperature
(7), heat up to finish after, treat that furnace temperature is cooled to room temperature, the described product that will carry out charing takes out, and uses the distilled water clean surface, till water for cleaning is limpid; Described product after cleaning is put into baking oven once more dry, promptly obtain mesh structural porous carbide carrier.
(8), described material with photocatalytic activity is become uniform suspension with the deionized water sonic oscillation, and add percentage by weight be 2%~3% KP1 as bonding agent, then this suspension evenly is coated on (7) resulting mesh structural porous carbide carrier; With load have the mesh structural porous carbide carrier of the material of photocatalytic activity, at 100~300 ℃ of freeze-day with constant temperature 2~3h, promptly obtain the single regular catalyst of plane network structure or space network.
17, the preparation method of regular catalyst as claimed in claim 16 is characterized in that: it also includes following step:
By at least one load have a photocatalytic activity material, described plane netted porous charcoal thing carrier or described solid netted porous carbide carrier, a single regular integral body of composition;
Or by at least one load have a mesh structural porous carbide carrier of quadrangular plan of photocatalytic activity material, be parallel to each other successively with the solid netted porous carbide carrier of quadrangle chevron-shaped and stack, between the netted porous charcoal thing carrier of the described plane of every adjacent two layers, do supporter with the solid netted porous carbide carrier of the described quadrangle chevron-shaped of one deck, the vertical plane of the solid netted porous carbide carrier of wherein said quadrangle chevron-shaped is identical with the vertical plane size of the mesh structural porous carbide carrier of described quadrangular plan, the shape unanimity; The shortest limit of described plane netted porous charcoal thing carrier is 10~20: 1 with the ratio of the described plane of adjacent two layers netted porous charcoal thing carrier distance, and contact point is fixed and formed a regular integral body between adjacent layer;
Or by at least one load have an identical shaped described triangle of photocatalytic activity material, polygon, circular, or the plane of irregular abnormity netted porous charcoal thing carrier, the placement that is parallel to each other successively of different plane, average every meter quantity that comprises catalyst is 1~30, is fixed by shell and forms a regular integral body;
Or by at least one load have an identical shaped described taper shape of photocatalytic activity material, or pyramid or truncated cone-shaped, or the solid netted porous carbide carrier of terrace with edge shape, along the placement that is parallel to each other successively of coaxial line direction, average every meter conial vertex number that comprises is 1~30, is fixed by shell and forms a regular integral body; The solid netted porous carbide carrier of described truncated cone-shaped or terrace with edge shape, its upper bottom surface and bottom surface also are porous network structure;
Or by at least one load have the described cylindrical of photocatalytic activity material, prismatic solid netted porous carbide carrier, choose highly identical, the described load that diameter does not wait have the cylindrical of photocatalytic activity material, prismatic solid netted porous carbide carrier, fix and form a regular integral body by the ascending order of diameter suit successively, its adjacent parallel interplanar distance greater than zero less than outermost layer cylinder or prismatic diameter.
CNB2006100779590A 2006-04-27 2006-04-27 Catalyst carbide carrier and its preparation method, regular catalyst and its preparation method Expired - Fee Related CN100400160C (en)

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CN105135660A (en) * 2015-09-01 2015-12-09 天津贝罗尼生物科技有限公司 Cold contact agent filter screen for air purifier
CN106057266A (en) * 2016-05-23 2016-10-26 中国工程物理研究院材料研究所 Photocatalytic digestion method for carbon material
CN106238059A (en) * 2016-07-13 2016-12-21 中国科学院化学研究所 A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system
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JP3981565B2 (en) * 2001-03-21 2007-09-26 守信 遠藤 Carbon fiber by vapor phase growth method supporting catalytic metal

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CN102728412A (en) * 2012-06-07 2012-10-17 江苏恒智纳米科技有限公司 Porous ceramic plate photocatalyst carrier
CN105135660A (en) * 2015-09-01 2015-12-09 天津贝罗尼生物科技有限公司 Cold contact agent filter screen for air purifier
CN105135660B (en) * 2015-09-01 2018-03-27 天津贝罗尼生物科技有限公司 A kind of cold catalyst screen pack for air purifier
CN106057266A (en) * 2016-05-23 2016-10-26 中国工程物理研究院材料研究所 Photocatalytic digestion method for carbon material
CN106238059A (en) * 2016-07-13 2016-12-21 中国科学院化学研究所 A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system
CN109455810A (en) * 2018-12-24 2019-03-12 河海大学 A kind of light-catalyzed reaction plate and the preparation method and application thereof
CN109455810B (en) * 2018-12-24 2021-05-11 河海大学 Photocatalytic reaction plate and preparation method and application thereof

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