阅读说明：本技术 一种多孔微通道的载体及其制备方法 (Carrier of porous micro-channel and preparation method thereof ) 是由 陈敏生 刘杰 范彦斌 郑泽锦 亢志颖 朱涛 于 2020-12-08 设计创作，主要内容包括：本发明提供了一种多孔微通道的载体,所述载体包括载体板以及设置在所述载体板一侧并与所述载体板一体成型的多个单元体,多个所述单元体包括第一凸台以及第二凸台,所述第一凸台与所述第二凸台均垂直于所述载体板并等间距分布；所述第一凸台与所述第二凸台交错设置且相互平行；所述第一凸台上设置有第一微孔,所述第二凸台上设置有第二微孔,且所述第一微孔以及所述第二微孔错开设置。本发明制备的载体具有多个单元体,且单元体上设置有第一微孔以及第二微孔,使得载体整体上具有较多的微孔通道,有效增加比表面积,使其具有显著的导热性能,有助于载体的层叠扩展。另外,制备的载体能增加催化剂的附着量和附着面积,提高反应的转化率。(The invention provides a carrier of a porous microchannel, which comprises a carrier plate and a plurality of unit bodies, wherein the unit bodies are arranged on one side of the carrier plate and are integrally formed with the carrier plate; the first bosses and the second bosses are arranged in a staggered manner and are parallel to each other; the first boss is provided with a first micropore, the second boss is provided with a second micropore, and the first micropore and the second micropore are arranged in a staggered mode. The carrier prepared by the invention is provided with a plurality of unit bodies, and the unit bodies are provided with the first micropores and the second micropores, so that the carrier has more micropore channels on the whole, the specific surface area is effectively increased, the carrier has remarkable heat-conducting property, and the carrier is beneficial to the stacking expansion of the carrier. In addition, the prepared carrier can increase the adhering amount and the adhering area of the catalyst and improve the conversion rate of the reaction.)

1. The carrier of the porous microchannel is characterized by comprising a carrier plate and a plurality of unit bodies which are arranged on one side of the carrier plate and are integrally formed with the carrier plate, wherein each unit body comprises a first boss and a second boss, and the first bosses and the second bosses are perpendicular to the carrier plate and are distributed at equal intervals; the first bosses and the second bosses are arranged in a staggered manner and are parallel to each other; the first boss is provided with a first micropore, the second boss is provided with a second micropore, and the first micropore and the second micropore are arranged in a staggered mode.

2. The carrier of claim 1, wherein the first pore comprises a first through hole and a second through hole, and the first through hole is in communication with the second through hole.

3. The carrier of claim 2, wherein the second micropores include a third through hole and a fourth through hole, and the third through hole is in communication with the fourth through hole.

4. A method for preparing a support for a porous microchannel according to any one of claims 1 to 3, comprising the steps of:

setting a porosity target value, and according to the formula:calculating the pore volume;

according to the formula: the volume of the unit body is determined as the total volume-pore volume;

adjusting the size and the position of the volume of the unit body so that the porosity of the unit body meets a target value;

checking whether the unit bodies meet the precision of laser printing equipment or not, and finishing the model design of the porous micro-channel carrier;

and (3) placing the metal powder in a laser printing device to print to obtain the porous microchannel carrier.

5. The method for preparing the carrier of the porous microchannel according to claim 4, wherein the laser printing apparatus comprises a controller, a forming chamber, a laser and a vibrating mirror arranged at the upper part of the forming chamber, a powder spreading device arranged in the forming chamber, and a first cavity, a second cavity and a third cavity which are arranged at the bottom of the forming chamber and are integrally formed with the forming chamber, and the controller is respectively connected with the laser, the vibrating mirror and the powder spreading device.

6. The method of claim 5, wherein a first plate is disposed in the first cavity, and a second plate is disposed in the second cavity.

7. The method for preparing a porous microchannel carrier according to claim 6, wherein the laser printing apparatus further comprises a first servo cylinder and a second servo cylinder, one end of the first servo cylinder is connected to the first plate, and the other end of the first servo cylinder is connected to the controller; one end of the second servo cylinder is connected with the second plate, and the second servo cylinder is connected with the controller.

8. The method of claim 7, wherein the first cavity is filled with the metal powder.

9. The method for preparing a carrier for a porous microchannel according to claim 8, wherein the printing method is:

a. the first servo cylinder drives the first plate to ascend, so that the metal powder in the first cavity is pushed into the forming chamber by the first plate;

b. the second servo cylinder drives the second plate to descend;

c. the powder spreading device moves from the first containing cavity to the second containing cavity, the metal powder is filled into the second containing cavity, and the redundant metal powder is pushed to the third containing cavity to be recycled;

d. controlling the laser to emit laser, and melting and molding the metal powder in the second cavity through the galvanometer;

e. controlling the laser to stop emitting laser light;

f. and circulating the steps until the printing is finished to prepare the carrier of the porous micro-channel.

10. The method of claim 9, wherein the first plate is raised to a height greater than or equal to a height of the second plate lowered.

Technical Field

The invention relates to the field of reaction carrier preparation, in particular to a carrier of a porous micro-channel and a preparation method thereof.

Background

With the development of new energy automobile industry becoming mature, the fuel cell technology as one of the realization ways is more and more emphasized, and thus the overall development of the hydrogen energy industry chain is driven. Hydrogen production by methanol reforming is one of the currently generally adopted methods, but the improvement of catalytic efficiency is always limited by the performance of a carrier carrying a catalyst. Therefore, the development of a catalytic carrier having high catalytic efficiency is a direction of practical value. At present, the method for preparing the catalytic carrier mainly comprises a foaming method, an oriented copper fiber sintering felt method and a milling method, but the reaction carrier prepared by the foaming method has low heat transfer efficiency, and the hole type aperture and the porosity of the porous micro-channel structure are uncontrollable; the reaction carrier prepared by the directional copper fiber sintered felt method has poor thermal conductivity, is not beneficial to the lamination expansion of the reaction carrier, and the hole type aperture and the porosity of the porous micro-channel structure are not controllable; the milling method makes it difficult to manufacture a reaction carrier having a porous microchannel structure with a complicated shape. Generally detrimental to catalyst adhesion and hydrogen conversion.

In summary, there still remains a need to solve the above problems in the field of reaction carrier preparation.

Disclosure of Invention

Based on the above, in order to solve the problems that the reaction carrier with a porous micro-channel structure with a complex shape is difficult to prepare, the heat transfer efficiency for preparing the reaction carrier is low, and the pore type pore size and the porosity of the porous micro-channel structure are difficult to control in the prior art, the invention provides a carrier of a porous micro-channel and a preparation method thereof, and the specific technical scheme is as follows:

a carrier of a porous microchannel comprises a carrier plate and a plurality of unit bodies which are arranged on one side of the carrier plate and are integrally formed with the carrier plate, wherein each unit body comprises a first boss and a second boss, and the first bosses and the second bosses are perpendicular to the carrier plate and are distributed at equal intervals; the first bosses and the second bosses are arranged in a staggered manner and are parallel to each other; the first boss is provided with a first micropore, the second boss is provided with a second micropore, and the first micropore and the second micropore are arranged in a staggered mode.

The carrier in the scheme has a plurality of unit bodies, and the unit bodies are provided with the first micropores and the second micropores, so that the carrier integrally has more micropore channels, the specific surface area is effectively increased, the carrier has remarkable heat-conducting performance, and the carrier is favorable for stacking and expanding. In addition, the prepared carrier can increase the adhering amount and the adhering area of the catalyst and improve the conversion rate of the reaction.

Preferably, the first micro-hole includes a first through-hole and a second through-hole, and the first through-hole communicates with the second through-hole.

Preferably, the second micro-hole includes a third through hole and a fourth through hole, and the third through hole communicates with the fourth through hole.

In addition, the invention also provides a preparation method of the carrier of the porous microchannel, which comprises the following steps:

setting a porosity target value, and according to the formula:calculating the pore volume;

according to the formula: the volume of the unit body is determined as the total volume-pore volume;

adjusting the size and the position of the volume of the unit body so that the porosity of the unit body meets a target value;

checking whether the unit bodies meet the precision of laser printing equipment or not, and finishing the model design of the porous micro-channel carrier;

and (3) placing the metal powder in a laser printing device to print to obtain the porous microchannel carrier.

The preparation method of the carrier is simple in steps and high in feasibility, and the carrier with the porous micro-channel structure in the complex shape can be prepared through laser printing equipment, and the void type, the pore diameter and the porosity of the porous micro-channel structure are controllable.

Preferably, laser printing equipment includes controller, shaping room, sets up laser instrument and the mirror that shakes on shaping room upper portion, set up and be in powder paving device, the setting in the shaping room is in shaping room bottom and with shaping room integrated into one piece's first appearance chamber, second hold the chamber and the third holds the chamber, just the controller respectively with the laser instrument shake the mirror and the powder paving device is connected.

Preferably, a first plate is arranged in the first accommodating cavity, and a second plate is arranged in the second accommodating cavity.

Preferably, the laser printing apparatus further comprises a first servo cylinder and a second servo cylinder, one end of the first servo cylinder is connected with the first plate, and the other end of the first servo cylinder is connected with the controller; one end of the second servo cylinder is connected with the second plate, and the second servo cylinder is connected with the controller.

Preferably, the first cavity is filled with the metal powder.

Preferably, the printing method is as follows:

a. the first servo cylinder drives the first plate to ascend, so that the metal powder in the first cavity is pushed into the forming chamber by the first plate;

b. the second servo cylinder drives the second plate to descend;

c. the powder spreading device moves from the first containing cavity to the second containing cavity, the metal powder is filled into the second containing cavity, and the redundant metal powder is pushed to the third containing cavity to be recycled;

d. controlling the laser to emit laser, and melting and molding the metal powder in the second cavity through the galvanometer;

e. controlling the laser to stop emitting laser light;

f. and circulating the steps until the printing is finished to prepare the carrier of the porous micro-channel.

The printing method has remarkable printing accuracy, and can effectively control the hole pattern, the pore diameter and the porosity of the porous micro-channel structure in the carrier.

Preferably, the height of the first plate which rises is greater than or equal to the height of the second plate which falls.

Drawings

The invention will be further understood from the following description in conjunction with the accompanying drawings. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the embodiments. Like reference numerals designate corresponding parts throughout the different views.

FIG. 1 is a schematic diagram showing the structure of a carrier of a porous microchannel according to an embodiment of the present invention;

FIG. 2 is a second schematic structural view of a support of a porous microchannel according to an embodiment of the present invention;

FIG. 3 is a schematic diagram showing a part of the structure of a carrier of a porous microchannel in an embodiment of the present invention;

FIG. 4 is a schematic diagram of a second partial structure of a carrier of a porous microchannel according to an embodiment of the present invention;

FIG. 5 is a schematic diagram III of a portion of a support for a porous microchannel according to an embodiment of the present invention;

FIG. 6 is a schematic diagram of a part of a structure of a carrier of a porous microchannel in an embodiment of the invention;

fig. 7 is a schematic structural diagram of a laser printing apparatus in an embodiment of the present invention.

Description of reference numerals:

11. a carrier plate; 21. a first boss; 211. a first through hole; 212. a second through hole; 22. a second boss; 221. a third through hole; 222. a fourth via hole; 31. a controller; 41. a forming chamber; 411. a first cavity; 412. a second cavity; 413. a third cavity; 414. a first plate; 415. a second plate; 51. a laser; 61. a galvanometer; 71. a powder spreading device; 81. a first servo cylinder; 91. a second servo cylinder.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The terms "first" and "second" used herein do not denote any particular order or quantity, but rather are used to distinguish one element from another.

As shown in fig. 1 to 7, in one embodiment of the present invention, a porous microchannel carrier with controllable porosity,

the carrier comprises a carrier plate 11 and a plurality of unit bodies which are arranged on one side of the carrier plate 11 and are integrally formed with the carrier plate 11, wherein each unit body comprises a first boss 21 and a second boss 22, and the first bosses 21 and the second bosses 22 are perpendicular to the carrier plate 11 and are distributed at equal intervals; the first bosses 21 and the second bosses 22 are arranged in a staggered manner and are parallel to each other; the first boss 21 is provided with a first micropore, the second boss 22 is provided with a second micropore, and the first micropore and the second micropore are arranged in a staggered manner.

The carrier in the scheme has a plurality of unit bodies, the unit bodies are provided with the first micropores and the second micropores, the prepared carrier integrally has more micropore channels, the specific surface area is effectively increased, the carrier has remarkable heat-conducting performance, and the stacking expansion of the carrier is facilitated. In addition, the prepared carrier can increase the adhering amount and the adhering area of the catalyst and improve the conversion rate of the reaction.

In one embodiment, the first micro via includes a first through hole 211 and a second through hole 212, and the first through hole 211 communicates with the second through hole 212.

In one embodiment, the diameter of the first through hole 211 is greater than or equal to the diameter of the second through hole 212.

In one embodiment, the first through hole 211 is flared.

In one embodiment, the second through hole 212 is cylindrical.

In one embodiment, the second micro-hole includes a third through hole 221 and a fourth through hole 222, and the third through hole 221 is communicated with the fourth through hole 222.

In one embodiment, the diameter of the third through hole 221 is greater than or equal to the diameter of the fourth through hole 222.

In one embodiment, the third through hole 221 is flared.

In one embodiment, the fourth through hole 222 is cylindrical.

The specific size of the unit body, the specific positions and sizes of the first micropores, the second micropores, the first bosses and the second bosses can be changed according to different carrier porosities, so that the effect of porosity controllability is achieved.

In one embodiment, the largest dimension of the unit cell is 2 mm.

In one embodiment, the height of each of the first boss 21 and the second boss 22 is 1.6 mm.

In one embodiment, the thickness of each of the first boss 21 and the second boss 22 is 0.4 mm.

In one embodiment, the distance between the first boss 21 and the second boss 22 is 0.4 mm.

In one embodiment, the distance between the edge of the unit body parallel to the first bosses 21 and the first bosses 21 is 0.4mm or more.

In one embodiment, the distance between the edge of the unit cell parallel to the second bosses 22 and the second bosses 22 is 0.4mm or more.

In one embodiment, the maximum diameter of the first through hole 211 is 0.6 mm.

In one embodiment, the diameter of the second through hole 212 is 0.2 mm.

In one embodiment, the maximum diameter of the third through hole 221 is 0.6 mm.

In one embodiment, the diameter of the fourth through hole 222 is 0.2 mm.

In addition, the invention also provides a preparation method of the carrier of the porous microchannel, which comprises the following steps:

setting a porosity target value, and according to the formula: the porosity is the pore volume/total volume, and the pore volume is calculated;

according to the formula: the total volume of the unit body is the total volume-pore volume, and the total volume of the unit body is calculated;

adjusting the size and position of each unit body and the size and position of the first boss and the second boss on each unit body so that the porosity of each unit body meets a target value;

checking whether the unit bodies meet the precision of laser printing equipment or not, and finishing the model design of the porous micro-channel carrier;

slicing the STL file of the porous micro-channel carrier through slicing software, importing sliced data into path planning software for path planning, and exporting the path planning file of the porous micro-channel carrier with controllable porosity after path planning is finished;

importing a path planning file of a carrier into Selective Laser Melting (SLM) equipment, and setting printing parameters;

and (3) placing the metal powder in a laser printing device to print to obtain the porous microchannel carrier.

The preparation method of the carrier is simple in steps and high in feasibility, and the carrier with the porous micro-channel structure in the complex shape can be prepared through laser printing equipment, and the void type, the pore diameter and the porosity of the porous micro-channel structure are controllable.

In one embodiment, the laser printing apparatus includes a controller 31, a forming chamber 41, a laser 51, a galvanometer 61, a powder spreading device 71, a first cavity 411, a second cavity 412 and a third cavity 413, wherein the laser 51 and the galvanometer 61 are disposed above the forming chamber 41; the powder spreading device 71 is arranged in the forming chamber 41, the first accommodating cavity 411, the second accommodating cavity 412 and the third accommodating cavity 413 are arranged at the bottom of the forming chamber 41 and communicated with the forming chamber 41, and the controller 31 is respectively connected with the laser 51, the vibrating mirror 61 and the powder spreading device 71.

In one embodiment, a first plate 414 is disposed in the first cavity 411, and a second plate 415 is disposed in the second cavity 412.

In one embodiment, the laser printing apparatus further includes a first servo cylinder 81 and a second servo cylinder 91, one end of the first servo cylinder 81 is connected to the first plate 414, and the other end of the first servo cylinder 81 is connected to the controller 31; one end of the second servo cylinder 91 is connected to the second plate 415, and the second servo cylinder 91 is connected to the controller 31.

In one embodiment, the first receiving cavity 411 is filled with the metal powder.

In one embodiment, the printing method includes:

a. the first servo cylinder 81 drives the first plate 414 to ascend, so that the metal powder in the first cavity 411 is pushed into the forming chamber 41 by the first plate 414;

b. the second servo cylinder 91 drives the second plate 415 to descend;

c. the powder spreading device 71 moves from the first cavity 411 to the second cavity 412 to fill the metal powder into the second cavity 412, and the redundant metal powder is pushed to the third cavity 413 to be recycled;

d. controlling the laser 51 to emit laser, and irradiating the laser to the metal powder in the second cavity 412 through the vibrating mirror 61 to melt and mold the metal powder;

e. controlling the laser 51 to stop emitting laser light;

f. and circulating the steps until the printing is finished to prepare the carrier of the porous micro-channel.

The printing method has remarkable printing accuracy, and can effectively control the hole pattern, the pore diameter and the porosity of the porous micro-channel structure in the carrier.

In one embodiment, the first plate 414 rises to a height greater than or equal to the height of the second plate 415.

In one embodiment, the porous microchannel carrier is applied to a reactor for producing hydrogen by reforming methanol and water vapor. The carrier of the porous microchannel is applied to a reactor for producing hydrogen by reforming methanol steam, is used as a supported catalyst, has a larger specific surface area, effectively increases the attachment amount and the attachment area of the catalyst, further improves the conversion rate of hydrogen and improves the efficiency of the reaction for producing hydrogen by reforming methanol.

The first embodiment is as follows:

a preparation method of a carrier of a porous microchannel comprises the following steps:

setting a porosity target value, and according to the formula: the porosity is the pore volume/total volume, and the pore volume is calculated;

according to the formula: the volume of the unit body is determined as the total volume-pore volume;

adjusting the size and the position of the volume of the unit body so that the porosity of the unit body meets a target value;

checking whether the unit bodies meet the precision of laser printing equipment or not, and finishing the model design of the porous micro-channel carrier;

and (3) placing the metal powder in a laser printing device to print to obtain the porous microchannel carrier.

The carrier of the porous microchannel prepared in one embodiment comprises a carrier plate 11 and a plurality of unit bodies which are arranged on one side of the carrier plate 11 and are integrally formed with the carrier plate 11, wherein the plurality of unit bodies comprise first bosses 21 and second bosses 22, and the first bosses 21 and the second bosses 22 are perpendicular to the carrier plate 11 and are distributed at equal intervals; the first bosses 21 and the second bosses 22 are arranged in a staggered manner and are parallel to each other; the first boss 21 is provided with a first micropore, the second boss 22 is provided with a second micropore, the first micropore and the second micropore are arranged in a staggered manner, the first micropore comprises a first through hole 211 and a second through hole 212, the first through hole 211 is communicated with the second through hole 212, and the diameter of the first through hole 211 is larger than or equal to that of the second through hole 212; the second micro-hole comprises a third through hole 221 and a fourth through hole 222, the third through hole 221 is communicated with the fourth through hole 222, and the diameter of the third through hole 221 is larger than or equal to that of the fourth through hole 222.

The size of the unit cell of the porous microchannel carrier prepared in example one was 2mm by 2 mm; the heights of the first boss 21 and the second boss 22 are both 1.6 mm; the thicknesses of the first boss 21 and the second boss 22 are both 0.4 mm; the distance between the first boss 21 and the second boss 22 is 0.4 mm; the maximum diameter of the first through hole 211 is 0.6 mm; the diameter of the second through hole 212 is 0.2 mm; the maximum diameter of the third through hole 221 is 0.6 mm; the diameter of the fourth through hole 222 is 0.2 mm.

The porosity of the carrier of the porous microchannel obtained was 62.3%.

The thermal conductivity of the porous microchannel carrier prepared in example was measured by the test method of measuring thermal diffusivity by the flash method according to ASTM E1461-13, and the result showed that the porous microchannel carrier prepared in example one had a remarkable thermal conductivity.

The carrier of the porous microchannel prepared in the first embodiment is applied to a reactor for producing hydrogen by reforming methanol steam, and the conversion rate of the obtained hydrogen is more than 90%.

In one embodiment, the reactor is an ultrasonic-assisted methanol steam reforming hydrogen production reactor, and the pressure of high-temperature high-pressure saturated steam in the reforming hydrogen production reactor is 6MPa-10MPa, and the temperature of the high-temperature high-pressure saturated steam is 275-310 ℃.

In conclusion, the carrier of the porous microchannel prepared by the invention has the advantages of controllable void ratio, excellent heat-conducting property and capability of effectively improving the hydrogen conversion rate.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.