CN111185125A

CN111185125A - Device and method for activating deactivated catalyst

Info

Publication number: CN111185125A
Application number: CN202010020562.8A
Authority: CN
Inventors: 刘泰秀; 刘启斌; 郑志美; 隋军
Original assignee: Institute of Engineering Thermophysics of CAS
Current assignee: Institute of Engineering Thermophysics of CAS
Priority date: 2020-01-08
Filing date: 2020-01-08
Publication date: 2020-05-22
Anticipated expiration: 2040-01-08
Also published as: CN111185125B

Abstract

The present disclosure provides an apparatus for deactivated catalyst activation, comprising: the gas distribution unit is used for conveying reducing gas with adjustable concentration, temperature and flow; the system comprises a plurality of groups of solar thermochemical reactor units, a plurality of groups of solar thermochemical reactor units and a plurality of heat exchange units, wherein the plurality of groups of solar thermochemical reactor units are fixedly arranged on a rack, each group of solar thermochemical reactor units comprise a plurality of solar thermochemical reactors which are arranged in parallel and filled with catalysts, and electric heating wires are arranged in catalyst beds and used for adjusting the temperature; and the gas transmission pipeline is used for connecting the gas distribution unit and the multiple groups of solar thermal chemical reactor units, and is provided with a valve for controlling the gas path flow of the multiple groups of solar thermal chemical reactor units so as to activate the catalysts in the multiple solar thermal chemical reactors in batches.

Description

Device and method for activating deactivated catalyst

Technical Field

The disclosure relates to the technical field of catalysts and reduction thereof, and particularly relates to a device and a method for activating an inactivated catalyst applied to a solar thermochemical utilization process.

Background

With the continuous development of economic society, the great consumption of fossil energy sources leads to the increasing exhaustion of energy sources and environmental pollution. Renewable energy sources are vigorously developed, and the development of clean energy sources is concerned widely. The solar fuel conversion is an important utilization technology of emerging renewable energy, the fuel is prepared from medium-low temperature solar energy, the solar thermochemical efficiency is high, the solar fuel can be thermochemically complemented with fossil fuel, and the solar energy fuel conversion has a good application prospect.

In the solar thermochemical utilization process, a catalyst is required to accelerate the thermochemical reaction process, the catalyst needs to be reduced and activated before being put into use, and the activated catalyst needs to be isolated from oxygen so as to prevent the catalyst from being reduced and disabled. Therefore, the catalyst needs to be filled first and then activated by reduction, that is, the catalyst is filled in the solar thermochemical reactor in advance and then activated by reduction. For a solar thermal chemical reactor, in order to reduce the heat loss to the environment and improve the conversion efficiency of solar energy, a vacuum thermal insulation layer is usually disposed on the solar thermal chemical reactor.

The catalyst needs to be maintained at a certain temperature for reduction and activation, and for a solar thermochemical reactor provided with a vacuum heat insulation layer, a catalyst bed layer is difficult to be heated in a heat exchange mode to meet the reduction requirement. The traditional catalyst activation method is to converge solar rays to a solar thermochemical reactor through a solar heat collector, and then heat a catalyst bed layer by using solar heat. However, the temperature of the catalyst bed is not uniform due to the nonuniform distribution of the energy flow density of the solar light-gathering and heat-collecting energy, and cannot be maintained at the temperature required by the reduction activation of the catalyst, so that the catalyst is not completely activated, and the local temperature is easily overhigh in the activation process, thereby causing the sintering of the catalyst. In addition, because the solar irradiation changes greatly along with the environment, the heat collection temperature is unstable, the activation process of the catalyst is difficult to control, and the reduction sintering failure of the catalyst is easily caused.

BRIEF SUMMARY OF THE PRESENT DISCLOSURE

Technical problem to be solved

Based on the problems, the disclosure provides a device and a method for activating an inactivated catalyst, so as to relieve the problems that in the prior art, when a catalyst bed layer is heated by solar heat energy in a solar thermochemical reactor for catalyst reduction, the temperature of the catalyst bed layer is not uniform due to nonuniform distribution of solar light-gathering and heat-collecting energy flow density, the temperature required by catalyst reduction and activation cannot be maintained, further the catalyst is not completely activated, and the local temperature is easily overhigh in the activation process, so that the catalyst is sintered; or the solar radiation is greatly changed along with the environment, the heat collection temperature is unstable, the activation process of the catalyst is difficult to control, and the reduction sintering failure of the catalyst is easy to cause.

(II) technical scheme

In one aspect of the present disclosure, there is provided an apparatus for deactivating catalyst activation, comprising:

the gas distribution unit is used for conveying reducing gas with adjustable concentration, temperature and flow;

the solar energy thermochemical reactor comprises a rack, a plurality of solar energy thermochemical reactor units and a plurality of heat exchange units, wherein the rack is used for connecting and fixing the plurality of groups of solar energy thermochemical reactor units, and each group of solar energy thermochemical reactor units comprise a plurality of solar energy thermochemical reactors which are arranged in parallel and filled with catalysts; the rack comprises a plurality of groups of electric heating wires which are respectively and correspondingly arranged in the catalyst bed layer in the solar thermochemical reactor and used for adjusting the temperature of the catalyst bed layer;

and the gas transmission pipeline is used for connecting the gas distribution unit and the multiple groups of solar thermal chemical reactor units, and is provided with a valve for controlling the gas path flow of the multiple groups of solar thermal chemical reactor units so as to activate the catalysts in the multiple solar thermal chemical reactors in batches.

In an embodiment of the present disclosure, the air distribution unit includes:

the gas source is used for providing reducing gas with adjustable concentration and flow; and

and the gas heater is connected with the gas source and used for heating the reducing gas.

In an embodiment of the present disclosure, the gantry further includes:

a temperature sensor buried in the catalyst bed layer; and

and the power regulator is connected with the electric heating wires and is used for regulating the heating power of the electric heating wires.

In the embodiment of the disclosure, the device for activating the deactivated catalyst further includes a control module, configured to collect a temperature signal of the temperature sensor, and control the power regulator and the gas distribution unit to regulate the heating power and the concentration and flow rate of the reducing gas.

In an embodiment of the present disclosure, the reducing gas includes: hydrogen, nitrogen or mixtures thereof.

In the embodiment of the disclosure, the temperature sensors are respectively arranged at two ends of the reactor body, and the measuring points of the temperature sensors are all embedded in the catalyst bed layer.

In the embodiment of the disclosure, the electric heating wires are uniformly embedded in the catalyst bed layer along the axial direction.

In another aspect of the present disclosure, there is provided a method of deactivating catalyst activation by a deactivated catalyst activation apparatus as described in any one of the above, the method of deactivating catalyst activation comprising:

step S1: the gas circuit connection among the multiple groups of solar thermochemical reactor units is adjusted to be in series connection by opening and closing the adjusting valve, and gas is supplied to the multiple groups of solar thermochemical reactor units through the gas distribution unit;

step S2: the gas circuit connection among the multiple groups of solar thermochemical reactor units is adjusted to be parallel connection by opening and closing the adjusting valve, and gas is continuously supplied to the multiple groups of solar thermochemical reactor units through the gas distribution unit; and

step S3: and (4) changing the flow direction of the gas supply path by adjusting the opening and closing of the valve, and repeating the steps S1 and S2 to ensure that the catalyst is completely reduced.

(III) advantageous effects

According to the technical scheme, the device and the method for activating the deactivated catalyst have at least one or part of the following beneficial effects:

(1) the reaction temperature is easy to control by adopting an electric heating mode, and the sintering of the catalyst is not caused.

(2) The electric heating wires are uniformly arranged in the axial direction and the circumferential direction, so that the solar thermochemical reactor is uniformly heated, and large heat exchange temperature difference and insufficient local reduction cannot be caused.

(3) And a mode of introducing reducing gas from two sides is adopted, so that the catalyst is activated more thoroughly.

(4) The solar thermochemical reactors are arranged on the catalyst reduction rack in parallel, so that the synchronous reduction of the catalysts in the solar thermochemical reactors is realized, and the activation time of the catalysts is shortened.

Drawings

FIG. 1 is a schematic diagram of the system components of an apparatus for deactivating catalyst activation according to an embodiment of the present disclosure.

Fig. 2 is a schematic diagram of a specific structure of a deactivated catalyst activation device according to an embodiment of the disclosure.

Fig. 3 is a schematic structural diagram of the solar thermochemical reactor in the embodiment of the disclosure in fig. 1.

Fig. 4 is a schematic structural diagram of an electric heating wire support frame according to an embodiment of the present disclosure.

FIG. 5 is a schematic flow diagram of a deactivated catalyst activation method according to an embodiment of the disclosure.

[ description of main reference numerals in the drawings ] of the embodiments of the present disclosure

10-a solar thermochemical reactor; 11-a gas source; 12-a gas heater;

13-a power regulator; 14-a reactor body; 15-a temperature sensor; 16-a control module;

20-electric heating wire support frame; 21-an electric heating wire; 30 stands.

Detailed Description

The present disclosure provides a device and a method for activating a deactivated catalyst, which are configured to reduce the catalyst in a straight-through solar thermal chemical reactor, and the solar thermal chemical reactor is often configured with a vacuum thermal insulation layer, so that the catalyst cannot be heated from the outside of the reactor in a heat conduction manner. The device and the method aim at realizing uniform distribution and regulation control of the temperature of a catalyst bed layer by regulating the electric heating power, and introducing nitrogen and hydrogen with certain concentration to realize efficient and sufficient reduction of the catalyst, improve the reduction quality of the catalyst and further improve the solar thermochemical conversion performance; the method is suitable for the type of the catalyst reduced by reducing gas, is easy to operate and has good catalyst activation effect.

For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.

In an embodiment of the present disclosure, there is provided a deactivated catalyst activation apparatus, as shown in fig. 1 to 4, including:

The gas distribution unit comprises:

the gas source is used for providing reducing gas with adjustable concentration; and

The rack, still include:

a temperature sensor buried in the catalyst bed layer; and

The device for activating the deactivated catalyst further comprises a control module which is used for collecting the temperature signal of the temperature sensor and controlling the power regulator and the gas distribution unit to regulate the heating power and the concentration and the flow of the reducing gas according to the temperature signal. And controlling the reaction process in the solar thermochemical reactor to make the temperature of the catalyst bed reach the optimal reduction temperature.

The catalyst comprises: catalysts requiring reductive activation, e.g. Cu-based catalysts (CuO/ZnO/Al)₂O₃)。

The reducing gas includes: hydrogen, nitrogen or mixtures thereof.

For a straight pipe type solar thermochemical reactor, temperature sensors are respectively arranged at the two ends of the inlet and the outlet of the straight pipe type solar thermochemical reactor, and measuring points of the temperature sensors are embedded in a catalyst bed layer.

The electric heating wires (single or multiple) are embedded in the catalyst bed layer in advance along the axial direction, and the electric heating wires are uniformly kept in the radial direction and the axial direction so as to ensure the temperature uniformity of the catalyst bed layer in the electric heating process.

The plurality of solar thermochemical reactors arranged in parallel are fixedly installed through a rack. As shown in fig. 2, the device for activating the deactivated catalyst has A, B two solar thermal chemical reactor units fixed on the rack, each solar thermal chemical reactor unit is composed of 3 solar thermal chemical reactors in parallel, and the flow of the reducing gas is controlled by switching the valve.

In an embodiment of the present disclosure, there is also provided a method for activating a deactivated catalyst, in which a catalyst is activated by using the apparatus for activating a deactivated catalyst, as shown in fig. 5, the method for activating a deactivated catalyst includes:

In the specific embodiment of the present disclosure, as shown in FIG. 1, the substrate will be filled with CuO/ZnO/Al₂O₃Reductive activation of catalyst in linear solar thermochemical absorption reactor. Three electric heating wires are arranged in the reactor side by side according to the mode shown in figure 2, and the electric heating wires are uniformly arranged in the catalyst bed layer in the axial direction and the circumferential direction. The plurality of solar thermochemical reactors are connected in parallel to form a solar thermochemical absorption/reaction unit. Through adjusting the valve, the switching of the serial connection and parallel connection of each solar thermochemical absorption/reaction unit is realized, and the flow direction of the reducing gas in the catalyst bed layer is adjusted. Reducing gases (H2 and N2) are configured through a gas source 11, preheated to a certain temperature through a gas heat collector 12 and then introduced into a solar thermochemical reactor 14; the heating power of the electric heating wire 21 is adjusted through the power adjuster 13, so that the catalyst bed layer is heated; the temperature sensor 15 detects the temperature of the catalyst bed in real time and transmits the detected temperature to the control module 16, and the control module 16 adjusts the power of the electric heating wire 21 and the flow of the reducing gas of the gas source 11 by feedback adjustment of the power regulator 13 and the gas distribution unit, so that the temperature of the catalyst bed reaches the optimal reducing temperature.

The signal is transmitted to a control module, and the control module controls the reaction process in the reactor by adjusting the power regulator and the gas distribution unit.

Fig. 3 is a support frame of resistance wire, the reactor is a straight-through pipe type, the support frame is placed with the circle center of the reactor as an axis, and three heating wires pass through holes preset on the support frame, so that the electric heating wires 21 are uniformly arranged inside the catalyst bed layer, and the temperature uniformity of the catalyst bed layer is improved.

The catalytic reduction process is divided into a plurality of stages, and as shown in fig. 2 and 5, in the initial catalyst reduction process, a valve 1, a valve A1, a valve A2, a valve B2 and a valve 3 are opened, a valve 2, a valve B1 and a valve 4 are closed, and a solar thermochemical absorption/reaction unit A, B is in a series structure; in the middle stage of catalyst reduction, the valve 1, the valve Al, the valve B1, the valve A2, the valve B2 and the valve 4 are opened, the valve 2 and the valve 3 are closed, and the solar thermochemical absorption/reaction unit A, B is in a parallel structure; in the later stage of catalyst reduction, the valve 2, the valve A2, the valve B2, the valve A1, the valve B1 and the valve 3 are opened, and the valve 1 and the valve 4 are closed so as to change the flow direction of hydrogen and nitrogen in the catalyst bed layer and ensure that the catalyst is completely reduced along each part of the process.

The present disclosure is applicable not only to CuO/ZnO/Al₂O₃This catalyst is also suitable for the type of catalyst activated with a reducing gas.

So far, the embodiments of the present disclosure have been described in detail with reference to the accompanying drawings. It is to be noted that, in the attached drawings or in the description, the implementation modes not shown or described are all the modes known by the ordinary skilled person in the field of technology, and are not described in detail. Further, the above definitions of the various elements and methods are not limited to the various specific structures, shapes or arrangements of parts mentioned in the examples, which may be easily modified or substituted by those of ordinary skill in the art.

In light of the above description, those skilled in the art will be clearly aware of the apparatus and method for deactivating catalyst activation of the present disclosure.

In summary, the present disclosure provides an apparatus and a method for activating an inactivated catalyst, wherein an electrical heating manner is adopted to provide heat for an activation process, and the reactor temperature is controlled by reasonably arranging heating wires, so as to further improve the activation degree of the catalyst and improve the solar energy utilization rate in a solar thermochemical process.

It should also be noted that directional terms, such as "upper", "lower", "front", "rear", "left", "right", and the like, used in the embodiments are only directions referring to the drawings, and are not intended to limit the scope of the present disclosure. Throughout the drawings, like elements are represented by like or similar reference numerals. Conventional structures or constructions will be omitted when they may obscure the understanding of the present disclosure.

And the shapes and sizes of the respective components in the drawings do not reflect actual sizes and proportions, but merely illustrate the contents of the embodiments of the present disclosure. Furthermore, in the claims, any reference signs placed between parentheses shall not be construed as limiting the claim.

Unless otherwise indicated, the numerical parameters set forth in the specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. In particular, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Generally, the expression is meant to encompass variations of ± 10% in some embodiments, 5% in some embodiments, 1% in some embodiments, 0.5% in some embodiments by the specified amount.

Furthermore, the word "comprising" does not exclude the presence of elements or steps not listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements.

The use of ordinal numbers such as "first," "second," "third," etc., in the specification and claims to modify a corresponding element does not by itself connote any ordinal number of the element or any ordering of one element from another or the order of manufacture, and the use of the ordinal numbers is only used to distinguish one element having a certain name from another element having a same name.

In addition, unless steps are specifically described or must occur in sequence, the order of the steps is not limited to that listed above and may be changed or rearranged as desired by the desired design. The embodiments described above may be mixed and matched with each other or with other embodiments based on design and reliability considerations, i.e., technical features in different embodiments may be freely combined to form further embodiments.

Those skilled in the art will appreciate that the modules in the device in an embodiment may be adaptively changed and disposed in one or more devices different from the embodiment. The modules or units or components of the embodiments may be combined into one module or unit or component, and furthermore they may be divided into a plurality of sub-modules or sub-units or sub-components. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and all of the processes or elements of any method or apparatus so disclosed, may be combined in any combination, except combinations where at least some of such features and/or processes or elements are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Also in the unit claims enumerating several means, several of these means may be embodied by one and the same item of hardware.

Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the disclosure, various features of the disclosure are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various disclosed aspects. However, the disclosed method should not be interpreted as reflecting an intention that: that is, the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, disclosed aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this disclosure.

The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims

1. An apparatus for deactivating catalyst activation comprising:

2. The deactivated catalyst activated device of claim 1, the gas distribution unit comprising:

3. The deactivated catalyst activated device of claim 1, the skid further comprising:

a temperature sensor buried in the catalyst bed layer; and

4. The apparatus for activating a deactivated catalyst according to claim 1, further comprising a control module for collecting a temperature signal from the temperature sensor and controlling the power regulator and the gas distribution unit to regulate the heating power and the concentration and flow rate of the reducing gas.

5. The deactivated catalyst activated device of claim 1, the reducing gas comprising: hydrogen, nitrogen or mixtures thereof.

6. The apparatus for activating a deactivated catalyst according to claim 3, wherein the temperature sensors are respectively disposed at two ends of the reactor body, and the measuring points of the temperature sensors are embedded in the catalyst bed.

7. An apparatus for deactivating catalyst activation according to claim 1, wherein the electric heating wire is uniformly embedded inside the catalyst bed in the axial direction.

8. A method of deactivated catalyst activation by the deactivated catalyst activation apparatus of any of claims 1 to 7, the method of deactivated catalyst activation comprising: