CN112973735A - Sulfur dioxide catalytic reduction self-vulcanization catalyst and preparation method thereof - Google Patents

Sulfur dioxide catalytic reduction self-vulcanization catalyst and preparation method thereof Download PDF

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CN112973735A
CN112973735A CN202110255555.0A CN202110255555A CN112973735A CN 112973735 A CN112973735 A CN 112973735A CN 202110255555 A CN202110255555 A CN 202110255555A CN 112973735 A CN112973735 A CN 112973735A
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sulfur dioxide
catalyst
catalytic reduction
sodium alginate
pyrite
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CN112973735B (en
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赵希强
田叶顺
马春元
冯太
夏霄
王涛
张立强
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Shandong University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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    • B01D53/8609—Sulfur oxides
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/32—Freeze drying, i.e. lyophilisation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a sulfur dioxide catalytic reduction self-vulcanizing catalyst and a preparation method thereof, wherein the sulfur dioxide catalytic reduction self-vulcanizing catalyst comprises the following steps: to be ultra-fineFully mixing the pyrite powder with the sodium alginate, adding deionized water, and uniformly stirring; dropping the mixed solution to CuCl2In solution in CuCl2Forming the sodium alginate-pyrite composite microspheres under the crosslinking action of the sodium alginate and the pyrite; and (3) carrying out hydrothermal carbonization or pyrolyzing the dried composite microspheres to obtain the catalyst.

Description

Sulfur dioxide catalytic reduction self-vulcanization catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a sulfur dioxide catalytic reduction self-vulcanizing catalyst and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Because the energy consumption structure of China always gives priority to coal for a long time, a large amount of sulfur dioxide with higher concentration is generated in the coal combustion process, and when the sulfur dioxide is directly discharged without being treated, the sulfur dioxide seriously harms the health and ecological environment of residents, the coal-fired flue gas needs to be comprehensively treated more thoroughly so as to meet the discharge standard.
The flue gas desulfurization method is mainly divided into a wet method and a dry method (including a semi-dry method), the limestone method is most widely applied in the wet method, the product of the method is desulfurized gypsum with low utilization value, the utilization rate of the desulfurized gypsum is low at present, the desulfurized gypsum is easy to be stacked as solid waste, the environment is polluted, and a large amount of space is occupied. In addition, the desulfurization product of part of (semi-) dry desulfurization method is sulfuric acid, which is liquid, and has the problems of inconvenient transportation and basically saturated domestic market supply.
In addition, the shortage of sulfur resources in China highly depends on import, and sulfur is a solid product with high added value, has the advantages of small capacity, no secondary pollution, no corrosion to equipment, convenience in storage and transportation and the like, and becomes an ideal desulfurization product. But instead of the other end of the tubeDue to the complex components in the flue gas, the oxygen and water vapor in the flue gas can deactivate the catalyst, resulting in SO2The reduction efficiency is greatly reduced, and SO2The reduction catalyst must be presulfided before use, and the process is complex and high in cost. In addition, the existing catalyst is difficult to recycle after being deactivated, thereby causing resource waste.
Disclosure of Invention
Aiming at the problems, the invention provides a sulfur dioxide catalytic reduction self-vulcanizing catalyst and a preparation method thereof.
To solve the above technical problem, one or more of the following embodiments of the present invention provide the following technical solutions:
in a first aspect, the present invention provides a method for preparing a sulfur dioxide catalytic reduction auto-sulfidation catalyst, comprising the following steps:
fully mixing the superfine pyrite powder with sodium alginate, adding deionized water, and uniformly stirring;
dropping the mixed solution to CuCl2In solution in CuCl2Forming the sodium alginate-pyrite composite microspheres under the crosslinking action of the sodium alginate and the pyrite;
and (3) carrying out hydrothermal carbonization or pyrolyzing the dried composite microspheres to obtain the catalyst.
In a second aspect, the invention provides a sulfur dioxide catalytic reduction auto-vulcanization catalyst, which is prepared by the preparation method.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
the superfine pyrite powder is adopted for uniformly distributing in the composite microspheres. Sodium alginate as cross-linking agent can provide carrier to fix pyrite and carbon source. In the pyrolysis process, the sodium alginate/pyrite co-pyrolysis is beneficial to expanding the pore structure of coke, increasing the specific surface area and reducing the temperature of converting pyrite into FeSx.
The invention is suitable for high-concentration SO in the sulfur-containing solid waste calcination, steel and non-ferrous metal smelting industry and the like2The resource desulfurization of the discharge industry not only canEffectively solve the problem of SO2O in the reduction process2The problem of catalyst deactivation caused by water vapor and the vulcanization process before the catalyst is used are also saved to ensure the reduction of the early SO2The reduction efficiency, in addition, the pore structure and the physical and chemical properties of the catalyst are improved, and the catalytic activity is greatly improved.
The carbon in the catalyst can react with O in the flue gas2The reaction not only eliminates the oxidation deactivation influence, but also provides CO required by the reduction reaction; the Cu ions loaded on the catalyst can effectively improve the water and CO resistance2The poisoning ability of (c); the catalyst is simple to prepare, a pre-vulcanization process is not needed, the process time and cost are saved to a great extent, and the SO in the earlier stage of reduction is improved2The conversion efficiency.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a FeS-based catalyst used in an embodiment of the present invention2A process flow diagram for preparing the catalyst by thermal decomposition-self-vulcanization.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the present invention provides a method for preparing a sulfur dioxide catalytic reduction auto-sulfidation catalyst, comprising the following steps:
fully mixing the superfine pyrite powder with sodium alginate, adding deionized water, and uniformly stirring;
dropping the mixed solution to CuCl2In solution in CuCl2Forming the sodium alginate-pyrite composite microspheres under the crosslinking action of the sodium alginate and the pyrite;
and (3) carrying out hydrothermal carbonization or pyrolyzing the dried composite microspheres to obtain the catalyst.
In some embodiments, the sodium alginate mass concentration is 1-5 wt.%.
In some embodiments, the particle size of the ultrafine pyrite is 100-150 meshes, and the particle size is too large, so that the ultrafine pyrite is not mixed uniformly and is not easy to form balls.
In some embodiments, the CuCl is2The mass concentration of the solution is 1-25 wt.%.
In some embodiments, the ultrafine pyrite powder is mixed with the sodium alginate and then subjected to ultrasonic oscillation for 5-10 hours to remove surface bubbles, so that the mixture is more uniform.
In some embodiments, the mixed solution is added dropwise to the CuCl2And standing for 10-24h after the solution is dissolved, so that Cu ions in the solution can be better adsorbed on the microspheres.
In some embodiments, the composite microspheres are dried by freeze drying, which does not affect the coalescence state of the microspheres and can preserve the original microspheres intact without compaction and agglomeration.
In some embodiments, the pyrolysis atmosphere in which the composite microspheres are pyrolyzed is 15-25 vol.% CO2The balance being N2。
Further, the temperature for pyrolyzing the composite microspheres is 400-800 ℃, and the time is 20-60 min.
In a second aspect, the invention provides a sulfur dioxide catalytic reduction auto-vulcanization catalyst, which is prepared by the preparation method.
Example 1
Weighing 4g of sodium alginate powder and 2g of pyrite powder, putting the sodium alginate powder and the pyrite powder into a 250ml beaker, fully mixing, adding the pyrite powder with the granularity of 100-150 meshes, and adding the mixture100ml of deionized water is put into an ultrasonic oscillator (the water bath temperature is 60 +/-5 ℃) to be oscillated for 6 hours, and the deionized water and the ultrasonic oscillator are mixed evenly to obtain a mixed solution. Then the mixed solution was added dropwise to 500ml of 10 wt.% CuCl at a flow rate of 5ml/min by means of a peristaltic pump2In the solution, the sodium alginate microspheres are obtained by crosslinking and are uniformly present in CuCl2Standing the solution at room temperature for 12h, and freeze-drying the microspheres in a vacuum freeze-dryer for 24 h. The resulting microspheres were then placed in a pyrolysis furnace with 20 vol.% CO2As carrier gas, the pyrolysis temperature is 600 ℃, the pyrolysis time is 45min, and the pyrolyzed sample is collected and screened by a 60-mesh screen for later use.
The specific surface area of the prepared catalyst is 280m2/g。
Weighing 5g of prepared catalyst, placing the catalyst in a laboratory reaction tower, introducing high-sulfur flue gas into the reaction tower, wherein the flow of the high-sulfur flue gas is 300ml/min, the temperature in the reaction tower is 700 ℃, the volume concentration of sulfur dioxide in the high-sulfur flue gas is 1.5%, the volume concentration of water vapor is 5%, and the flow speed of the high-sulfur flue gas is 300ml/min, so that the contact time of the high-sulfur flue gas and the catalyst is 0.63s, detecting the flue gas at the outlet of the reaction tower, wherein the concentration of sulfur dioxide in the treated flue gas is about 750ppm, and the removal efficiency of sulfur dioxide is about 95%. After the catalyst is continuously operated for 1 day, the removal efficiency of sulfur dioxide is 85 percent.
Example 2
Weighing 4g of sodium alginate powder and 2g of pyrite powder, putting the sodium alginate powder and the pyrite powder into a 250ml beaker, fully mixing, adding 100ml of deionized water, and putting the beaker into an ultrasonic oscillator (the water bath temperature is 60 +/-5 ℃) for oscillation for 6 hours to uniformly mix the mixture to obtain a mixed solution. Then the mixed solution was added dropwise to 500ml of 10 wt.% CuCl at a flow rate of 5ml/min by means of a peristaltic pump2In the solution, the sodium alginate microspheres are obtained by crosslinking and are uniformly present in CuCl2In the solution, it was left standing at room temperature for 12 minutes. And putting the obtained microspheres into a hydrothermal carbonization device, wherein the pyrolysis temperature is 300 ℃, the pyrolysis time is 45min, and collecting a pyrolyzed sample and sieving the pyrolyzed sample by a 80-mesh sieve for later use.
The specific surface area of the prepared catalyst is 300m2/g。
Weighing 5g of prepared catalyst, placing the catalyst in a laboratory reaction tower, introducing high-sulfur flue gas into the reaction tower, wherein the flow of the high-sulfur flue gas is 300ml/min, the temperature in the reaction tower is 700 ℃, the volume concentration of sulfur dioxide in the high-sulfur flue gas is 1.5%, the volume concentration of water vapor is 5%, and the flow speed of the high-sulfur flue gas is 300ml/min, so that the contact time of the high-sulfur flue gas and the catalyst is 0.63s, detecting the flue gas at the outlet of the reaction tower, wherein the concentration of sulfur dioxide in the treated flue gas is about 450ppm, and the removal efficiency of sulfur dioxide is 97%. After the catalyst is continuously operated for 1 day, the removal efficiency of sulfur dioxide is 85 percent.
Comparative example 1
The difference from example 1 is that: only sodium alginate in example 1 was replaced with HPMC (hydroxypropylmethylcellulose), and the rest was the same as in example 1.
The specific surface area of the prepared catalyst is 106m2/g。
The concentration of sulfur dioxide in the treated flue gas is 6100ppm, and the removal efficiency of the sulfur dioxide is 79.7%. After the catalyst is continuously operated for 1 day, the removal efficiency of the sulfur dioxide is 54 percent.
Comparative example 2
The difference from example 1 is that: only the "mixed solution of example 1 was again passed through a peristaltic pump at a flow rate of 5ml/min, and 500ml of 10 wt.% CuCl was dropwise added2In solution ", replace with" mix solution directly with 500ml of 10 wt.% CuCl2Solution mix ", the rest is the same as in example 1.
The specific surface area of the prepared catalyst is 130m2/g。
The concentration of sulfur dioxide in the treated flue gas is 5500ppm, and the removal efficiency of the sulfur dioxide is 81.7%. After the catalyst is continuously operated for 1 day, the removal efficiency of the sulfur dioxide is 58 percent.
Comparative example 3
The difference from example 1 is that: 2g of pyrite powder in example 1 was replaced with 1.9g of FeS2And (3) powder.
The concentration of sulfur dioxide in the treated flue gas is about 1300ppm, and the removal efficiency of the sulfur dioxide is 88%. After the catalyst is continuously operated for 1 day, the removal efficiency of sulfur dioxide is 75 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a sulfur dioxide catalytic reduction auto-vulcanization catalyst is characterized by comprising the following steps: the method comprises the following steps:
fully mixing the superfine pyrite powder with sodium alginate, adding deionized water, and uniformly stirring;
dropping the mixed solution to CuCl2In solution in CuCl2Forming the sodium alginate-pyrite composite microspheres under the crosslinking action of the sodium alginate and the pyrite;
and (3) carrying out hydrothermal carbonization or pyrolyzing the dried composite microspheres to obtain the catalyst.
2. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: the mass concentration of sodium alginate is 1-5 wt.%.
3. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: the granularity of the superfine pyrite is 100-150 meshes.
4. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: CuCl2The mass concentration of the solution is 1-25 wt.%.
5. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: and mixing the superfine pyrite powder and the sodium alginate, and then carrying out ultrasonic oscillation for 5-10 h.
6. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: dropping the mixed solution to CuCl2Standing for 10-24h after the solution is added.
7. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: the method for drying the composite microspheres is freeze drying.
8. The method for preparing a sulfur dioxide catalytic reduction auto-sulfiding catalyst as recited in claim 1, wherein: the pyrolysis atmosphere for pyrolyzing the composite microspheres is 15-25 vol.% CO2The balance being N2。
9. The method of claim 8, wherein the sulfur dioxide is catalytically reduced from the sulfided catalyst, and wherein: the temperature for pyrolyzing the composite microspheres is 400-800 ℃, and the time is 20-60 min.
10. A sulfur dioxide catalytic reduction self-vulcanizing catalyst is characterized in that: prepared by the preparation method of any one of claims 1 to 9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1321515A (en) * 1970-04-16 1973-06-27 Sherritt Gordon Mines Ltd Production of sulphur from iron sulphide and sulphur dioxide
CN85104062A (en) * 1985-05-22 1986-07-16 太原工业大学 Catalytic desulfurizing agent for flue gas and preparation method thereof
CN102357364A (en) * 2011-09-05 2012-02-22 青岛科技大学 Preparation of activated carbon-based catalyst used for selective reduction desulphurization of flue gas
CN104096585A (en) * 2014-06-25 2014-10-15 四川大学 Carbon-based desulfurization catalyst for catalyzing and oxidating sulfur dioxide at low temperature as well as preparation and application thereof
EP2955775A1 (en) * 2014-06-10 2015-12-16 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Berlin Method of fabricating mesoporous carbon coated FeS2, mesoporous carbon coated FeS2, positive electrode material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1321515A (en) * 1970-04-16 1973-06-27 Sherritt Gordon Mines Ltd Production of sulphur from iron sulphide and sulphur dioxide
CN85104062A (en) * 1985-05-22 1986-07-16 太原工业大学 Catalytic desulfurizing agent for flue gas and preparation method thereof
CN102357364A (en) * 2011-09-05 2012-02-22 青岛科技大学 Preparation of activated carbon-based catalyst used for selective reduction desulphurization of flue gas
EP2955775A1 (en) * 2014-06-10 2015-12-16 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Berlin Method of fabricating mesoporous carbon coated FeS2, mesoporous carbon coated FeS2, positive electrode material
CN104096585A (en) * 2014-06-25 2014-10-15 四川大学 Carbon-based desulfurization catalyst for catalyzing and oxidating sulfur dioxide at low temperature as well as preparation and application thereof
CN109650513A (en) * 2018-12-29 2019-04-19 绍兴文理学院 A kind of complex class fenton catalyst and pollution treatment method based on modification biological charcoal

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* Cited by examiner, † Cited by third party
Title
UCAR DENIZ等: "Sequential precipitation of Cu and Fe using a three-stage sulfidogenic fluidized-bed reactor system", 《MINERALS ENGINEERING》 *

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