CN115715971A - Blast furnace gas desulfurization adsorbent and preparation method thereof - Google Patents
Blast furnace gas desulfurization adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a blast furnace gas desulfurization adsorbent based on faujasite and a preparation method thereof, which is characterized in that in an ethanol solution system of the faujasite, in the presence of a cetyl trimethyl ammonium halide template agent, tetraethoxysilane and ammonia water are used as reactants to synthesize nano silicon dioxide particles to coat on the surface of the faujasite, and after the template agent is removed by roasting, the desulfurization adsorbent with a core-shell structure is prepared. The invention improves the adsorption capacity of the desulfurization adsorbent on blast furnace gas hydrogen sulfide by regulating the surface structure of the faujasite, and improves the sulfur capacity of the desulfurization adsorbent.
Description
Technical Field
The invention belongs to the technical field of blast furnace gas purification, relates to a desulfurization adsorbent for blast furnace gas, and particularly relates to a zeolite desulfurization adsorbent for removing hydrogen sulfide in blast furnace gas and a preparation method of the desulfurization adsorbent.
Background
China is the first country with large iron production in the world and is also rich in a large amount of blast furnace gas. Blast furnace gas has wide application and is also an important energy resource. However, the presence of sulphides in the blast furnace gas can be very troublesome for its subsequent use, and the combustion process can produce SO 2 And the environment is polluted.
The tail SO of the working procedures of a blast furnace hot blast stove, a steel rolling heat treatment furnace and the like required by the national environmental protection agency at present 2 The discharge concentration is lower than 50mg/m 3 . The blast furnace gas is mainly used as a heat source in the above procedures, and sulfides in the blast furnace gas are removed from the source, so that the method has advantages compared with a tail end treatment scheme with multiple dispersed procedures.
Compared with coke oven gas, the blast furnace gas has large gas amount, large temperature and pressure fluctuation, and high CO content 2 、H 2 O and O 2 Therefore, the general coke oven gas desulfurization method cannot be directly applied to the desulfurization of blast furnace gas.
The industrially applied technology of blast furnace gas fine desulfurization mainly comprises hydrolysis and alkali liquor absorption and hydrolysis and metal oxide adsorption. The hydrolysis and the alkali liquor absorption are used for hydrolyzing and converting COS in the blast furnace gas into H under the action of a hydrolysis catalyst 2 S, the desulfurization technology of converting the sodium sulfide into NaSH by using alkali liquor for absorption has the advantage of large treatment capacity, but generates desulfurization waste salt, and in addition, the alkali liquor can be mixed with CO in the coal gas 2 The consumption of alkali liquor is large and the operation and maintenance cost is high due to the reaction; the lower the water content of the blast furnace gas is, the higher the temperature of the hot blast stove is required, so the wet desulphurization can also reduce the calorific value of the blast furnace gas. Therefore, the dry desulfurization of blast furnace gas has more prospect.
The hydrolysis and metal oxide adsorption are also that the hydrolysis conversion of COS is carried out firstly, and then metal oxides such as ferric oxide are adopted to carry out H 2 S is adsorbed, so that the method has the advantage of low one-time investment, but the metal oxide adsorbs H 2 The S can be converted into metal sulfide which is difficult to regenerate in the process, so that the metal oxide adsorbent which is saturated in adsorption needs to be periodically disassembled and replaced, and the industrial production efficiency is inevitably reduced greatly. In addition, the generated metal sulfide is hazardous waste, is easy to spontaneously combust and has larger potential safety hazard.
In order to break the bottleneck of the desulfurization technology, zeolite is usually used for adsorbing hydrogen sulfide. The zeolite has excellent regeneration performance, the operation cost of the desulfurization process is low, the desulfurization precision is high, the zeolite can be used for the subsequent removal of hydrogen sulfide of blast furnace gas, and various indexes of the zeolite are continuously optimized and improved through continuous improvement, but the zeolite still cannot meet the requirements.
RONG C, CHU D, HOPKINS J. Et al (Test and characterization of sodium zeolite supported gas phase depletion disorders [ Z ]]2009.) report on 0.1% H 2 S-50%H 2 -10%H 2 Balance of O-He, 800 ℃ and space velocity of 80000h -1 Under the condition, the adsorption performance of the zeolite to hydrogen sulfide after one adsorption regenerationThe content of the adsorbent was 99% of the original content, but the amount of the adsorbent penetrated was only 26mg/100g of the adsorbent.
The metal modification is an effective method for improving the adsorption capacity of the zeolite, and CRESPO D, IG, WANG Y, and the like (Superior sorbent for natural gas desulfurization [ J ] 2008) report that the Cu (I) Y zeolite after metal modification has better hydrogen sulfide adsorption capacity. However, the regeneration of the modified Cu (I) Y zeolite becomes more difficult, and the complete regeneration can be realized only by reacting in air at 350 ℃ for 8 hours.
Therefore, in view of the current situation that the regeneration performance of the conventional faujasite desulfurization adsorbent is good but the sulfur capacity is low, it is necessary to modify the faujasite desulfurization adsorbent while maintaining the good regeneration performance thereof, so as to further increase the sulfur capacity of the desulfurization adsorbent.
Disclosure of Invention
The invention aims to provide a blast furnace gas desulfurization adsorbent based on zeolite and a preparation method thereof, which improve the adsorption capacity of the desulfurization adsorbent on blast furnace gas hydrogen sulfide and improve the breakthrough sulfur capacity of the desulfurization adsorbent by regulating the surface structure of faujasite.
The blast furnace gas desulfurization adsorbent is prepared by taking tetraethoxysilane and ammonia water as reactants to synthesize nano silicon dioxide particles to coat the surface of faujasite in an ethanol solution system of the faujasite and in the presence of a hexadecyl trimethyl ammonium halide template agent, and roasting to remove the template agent so as to prepare the desulfurization adsorbent with a core-shell structure.
The blast furnace gas desulfurization adsorbent is a composite material obtained by coating a silicon dioxide layer on the surface of the traditional faujasite. Compared with faujasite, the surface of the faujasite is coated with porous silicon, so that surface hydroxyl groups are increased, and the surface area and the volume of micropores are improved.
The faujasite with silicon-aluminum atomic ratio of 1.1-3.5 is preferably used in the present invention.
Wherein the dosage of the ethyl orthosilicate is 0.35 to 0.85 time of the mass of the faujasite.
Further, the amount of the cetyltrimethylammonium halide template used is preferably 0.3 to 0.9 times the mass of the faujasite.
Further, the cetyltrimethylammonium halide templating agent may be cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
Furthermore, the invention also provides a specific preparation method of the blast furnace gas desulfurization adsorbent, which comprises the following steps:
1) Adding the faujasite raw powder into a mixed solution of water and ethanol for uniform dispersion;
2) Adding ammonia water into the dispersion liquid, adding a hexadecyl trimethyl ammonium halide template agent, and reacting under stirring;
3) Continuously dropwise adding ethyl orthosilicate into the reaction liquid, and stirring for reaction;
4) And separating out a solid product, washing, drying and roasting to obtain the desulfurization adsorbent.
Further, in the preparation method of the present invention, the mass ratio of water to ethanol in the mixed solution of water and ethanol is preferably 1.3-2: 1.
Furthermore, it is preferable to add the faujasite raw powder into the mixed solution with the mass of 140 to 200 times of that of the faujasite raw powder to be uniformly dispersed.
Furthermore, in the preparation method, the dosage of the ammonia water is 1.5 to 3.5 times of the mass of the template agent.
Specifically, in the preparation method of the present invention, it is preferable that tetraethoxysilane is added dropwise to the reaction solution at a rate of 1 to 3mL/min to carry out the reaction.
More preferably, after the ethyl orthosilicate is dripped, stirring and reacting are continuously carried out for 4 to 8 hours.
Specifically, in the preparation method of the invention, the solid product is finally roasted for 4-6 h at 500-550 ℃ in an air atmosphere to prepare the desulfurization adsorbent.
More specifically, before roasting, the solid product needs to be washed for a plurality of times by deionized water and ethanol respectively, and then dried for 5 to 24 hours at the temperature of between 100 and 200 ℃.
In a fixed bed reactor, the desulfurization adsorbent prepared by the invention is used for carrying out desulfurization adsorption reaction on simulated blast furnace gas mixed with hydrogen sulfide, and tests show that the penetration time of the desulfurization adsorbent is more than 55min, the penetration sulfur capacity is not less than 70mg/100g, and the penetration sulfur capacity after 10 times of regeneration is not less than 98% of the original penetration sulfur capacity.
Drawings
FIG. 1 is a diagram of the preparation of desulfurization adsorbent for removing H in various examples and comparative examples 2 Total sulfur breakthrough curve at S.
FIG. 2 shows the regeneration of the desulfurization adsorbent prepared in example 1 to remove H 2 The breakthrough sulfur capacity of S.
Detailed Description
The following detailed description of the embodiments of the present invention is provided with reference to the accompanying drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
Unless otherwise specified, the production process, the experimental method or the detection method related to the embodiments of the present invention are all conventional methods in the prior art, and the names and/or the abbreviations thereof all belong to conventional names in the field, which are very clear and definite in the related fields of application.
The various instruments, equipments, raw materials or reagents used in the examples of the present invention are not particularly limited in their sources, and are all conventional products commercially available from normal commercial sources, and can be prepared by conventional methods well known to those skilled in the art.
Example 1.
Weighing 800mL of water and 600mL of absolute ethyl alcohol, uniformly mixing in a beaker to obtain a mixed solution, slowly adding 10g of faujasite with the silicon-aluminum atomic ratio of 2.2, and uniformly dispersing.
Then, 10mL of ammonia water is dropwise added into the beaker, 3.0g of hexadecyl trimethyl ammonium bromide is added, stirring reaction is carried out for 0.5h at normal temperature, 4.3mL of tetraethoxysilane is continuously dropwise added, and stirring reaction is carried out for 6h.
Filtering out a solid reaction product, repeatedly and alternately washing the solid reaction product to be neutral by using water and absolute ethyl alcohol, drying the solid reaction product for 8 hours at the temperature of 110 ℃, uniformly crushing the solid reaction product, heating the solid reaction product to 550 ℃ from room temperature at the heating rate of 2 ℃/min, and roasting the solid reaction product for 4 hours in an air atmosphere to prepare the desulfurization adsorbent.
And (3) putting 10.8mL of the prepared desulfurization adsorbent into a fixed bed reactor for desulfurization, pretreating for 3 hours at 200 ℃ in a nitrogen atmosphere, and cooling to 60 ℃ for desulfurization performance evaluation.
The simulated blast furnace gas was fed into the fixed bed reactor at a constant flow rate (composition 52.2% 2 ，24%CO，16%CO 2 ，5%H 2 O，2%H 2 ，0.5%O 2 ，0.3%CH 4 ). After the flow rate of the simulated blast furnace gas was stabilized, 300ppm of hydrogen sulfide was mixed into the simulated blast furnace gas, and the adsorption desulfurization reaction was performed.
The gas content change at the outlet of the fixed bed reactor was monitored on-line using chromatography, the result being shown as curve b in FIG. 1.
When the outlet sulfur content is defined to be more than 5ppm, the desulfurization adsorbent is penetrated, and the corresponding time is penetration time. The breakthrough time and the breakthrough sulfur capacity of the desulfurization adsorbent were calculated to be 67min and 84mg/100g, respectively.
Repeatedly regenerating and desulfurizing the desulfurizing adsorbent at an airspeed of 1000 h -1 The clean blast furnace gas at 200 ℃ is regenerated for 3 hours.
The specific test result is shown in fig. 2, in 10 times of regeneration adsorption experiments, the sulfur breakthrough capacity of the desulfurization adsorbent is between 82 and 86mg/100g, and the desulfurization adsorbent has good regeneration performance.
Example 2.
Weighing 800mL of water and 600mL of absolute ethyl alcohol, uniformly mixing in a beaker to obtain a mixed solution, and slowly adding 8g of faujasite with the silicon-aluminum atomic ratio of 1.1 for uniform dispersion.
Then, 12mL of ammonia water was added dropwise into the beaker, 2.4g of hexadecyltrimethylammonium bromide was added, stirring and reacting were carried out at normal temperature for 0.5h, then, 3.5mL of tetraethoxysilane was added dropwise continuously, and stirring and reacting were carried out for 6h.
Filtering out a solid reaction product, repeatedly and alternately washing the solid reaction product to be neutral by using water and absolute ethyl alcohol, drying the solid reaction product for 12 hours at the temperature of 120 ℃, uniformly crushing the solid reaction product, heating the solid reaction product to 550 ℃ from room temperature at the heating rate of 2 ℃/min, and roasting the solid reaction product for 4 hours in an air atmosphere to prepare the desulfurization adsorbent.
The desulfurization adsorbent prepared above was used to perform adsorption desulfurization according to the method of example 1, and the gas content change at the outlet of the fixed bed reactor was monitored on-line by using chromatography, and the results are shown as curve c in fig. 1, and the breakthrough time and breakthrough sulfur capacity of the desulfurization adsorbent were calculated to be 57min and 71mg/100g, respectively.
Example 3.
Weighing 800mL of water and 400mL of absolute ethyl alcohol, uniformly mixing in a beaker to obtain a mixed solution, slowly adding 10g of faujasite with the silicon-aluminum atomic ratio of 1.5, and uniformly dispersing.
Then, 9mL of ammonia water was added dropwise into the beaker, 3.0g of hexadecyltrimethylammonium bromide was added, stirring and reacting were carried out at normal temperature for 0.5h, then 4.3mL of tetraethoxysilane was added dropwise continuously, and stirring and reacting were carried out for 7h.
Filtering out a solid reaction product, repeatedly and alternately washing the solid reaction product to be neutral by using water and absolute ethyl alcohol, drying the solid reaction product for 6 hours at the temperature of 110 ℃, uniformly crushing the solid reaction product, heating the solid reaction product to 500 ℃ from room temperature at the heating rate of 2 ℃/min, and roasting the solid reaction product for 6 hours in an air atmosphere to prepare the desulfurization adsorbent.
The desulfurization adsorbent prepared above was used to perform adsorption desulfurization according to the method of example 1, and the gas content change at the outlet of the fixed bed reactor was monitored on-line by using chromatography, and the results are shown as curve d in fig. 1, and the breakthrough time and the breakthrough sulfur capacity of the desulfurization adsorbent were calculated to be 70min and 87mg/100g, respectively.
Comparative example 1.
The faujasite raw material with the silicon-aluminum atomic ratio of 2.2 in the example 1 is directly used as a desulfurization adsorbent, the adsorption desulfurization reaction is carried out according to the method in the example 1, the gas content change at the outlet of the fixed bed reactor is monitored on line by using a chromatograph, and the result is shown as a curve a in figure 1, and the breakthrough time and the breakthrough sulfur capacity of the desulfurization adsorbent are respectively 15min and 27mg/100g by calculation.
It can be seen that the breakthrough time and breakthrough sulfur capacity of the faujasite desulfurization sorbent are significantly less than the hydrogen sulfide breakthrough time and breakthrough sulfur capacity of the desulfurization sorbent of the various examples of the invention.
The parameters of specific surface area and pore structure of the desulfurization adsorbent of comparative example 1 and the desulfurization adsorbent of example 1 were examined, and the results are shown in table 1.
As can be seen from the data in table 1, the desulfurization adsorbent obtained by coating the silica layer on the surface of the faujasite according to the present invention has an improved microporous surface area and pore volume as compared to the faujasite. Thus, the breakthrough sulfur capacity was increased from 27mg/100g to 84mg/100g, which is a 2.1-fold increase.
Comparative example 2.
Measuring 800mL of water and 600mL of absolute ethyl alcohol, uniformly mixing in a beaker to obtain a mixed solution, dropwise adding 10mL of ammonia water into the beaker, then adding 3g of hexadecyl trimethyl ammonium bromide, stirring and reacting at normal temperature for 0.5h, then continuously dropwise adding 4.3mL of tetraethoxysilane, and stirring and reacting for 6h.
Filtering out a solid reaction product, repeatedly and alternately washing the solid reaction product to be neutral by using water and absolute ethyl alcohol, drying the solid reaction product for 8 hours at the temperature of 110 ℃, uniformly crushing the solid reaction product, heating the solid reaction product to 550 ℃ from room temperature at the heating rate of 2 ℃/min, and roasting the solid reaction product for 4 hours in an air atmosphere to prepare the desulfurization adsorbent.
The desulfurization adsorbent prepared above was used to perform adsorption desulfurization reaction according to the method in example 1, and the gas content change at the outlet of the fixed bed reactor was monitored on-line by using chromatography, and the results are shown as curve e in fig. 1, and the breakthrough time and the breakthrough sulfur capacity of the desulfurization adsorbent were calculated to be 7min and 9mg/100g, respectively.
Comparative example 2 the conditions were the same as in example 1 except that no faujasite was added, but the breakthrough time of the desulfurization adsorbent was much shorter than that of the desulfurization adsorbent of each example, and even smaller than that of the faujasite of comparative example 1.
The comparison shows that the invention modifies the faujasite, and the tetraethoxysilane is hydrolyzed and condensed on the surface of the faujasite in the alkaline environment to form silicon dioxide, so that the composite material is obtained by combination, the pore size distribution of the zeolite is improved, the specific surface area is increased, the desulfurization performance is further improved, and the better effect on the subsequent adsorption of the hydrogen sulfide in the blast furnace gas is achieved.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. A desulfurizing adsorbent for blast furnace gas is prepared through preparing the template agent by using ethyl orthosilicate and ammonia water as reactants, coating the template agent on the surface of octahedral zeolite, calcining, and removing the template agent.
2. The blast furnace gas desulfurization adsorbent according to claim 1, wherein the faujasite has a silicon-aluminum atomic ratio of 1.1 to 3.5.
3. The blast furnace gas desulfurization adsorbent according to claim 1, characterized in that the amount of the tetraethoxysilane is 0.35 to 0.85 times the mass of the faujasite.
4. The blast furnace gas desulfurization adsorbent according to claim 1, wherein the amount of the cetyltrimethylammonium halide template is 0.3 to 0.9 times the mass of the faujasite.
5. The blast furnace gas desulfurization sorbent according to claim 1 or 4, characterized in that the cetyltrimethyl ammonium halide template is cetyltrimethyl ammonium bromide or cetyltrimethyl ammonium chloride.
6. The method for preparing the blast furnace gas desulfurization adsorbent according to claim 1, comprising:
1) Adding the faujasite raw powder into a mixed solution of water and ethanol for uniform dispersion;
2) Adding ammonia water into the dispersion liquid, adding a hexadecyl trimethyl ammonium halide template agent, and reacting under stirring;
3) Continuously dropwise adding ethyl orthosilicate into the reaction liquid, and stirring for reaction;
4) And separating out a solid product, washing, drying and roasting to prepare the desulfurization adsorbent.
7. The preparation method of the desulfurization adsorbent for blast furnace gas according to claim 6, characterized in that faujasite raw powder is added into a mixed solution 140-200 times of the mass of the faujasite raw powder and uniformly dispersed, and the mass ratio of water to ethanol in the mixed solution is 1.3-2: 1.
8. The preparation method of the desulfurization adsorbent for blast furnace gas according to claim 6, wherein the amount of the ammonia water is 1.5 to 3.5 times of the mass of the template agent.
9. The preparation method of the desulfurization adsorbent for blast furnace gas according to claim 6, characterized in that tetraethoxysilane is dripped into the reaction solution at a speed of 1-3 mL/min for reaction, and after the tetraethoxysilane is dripped, the reaction is continued to be stirred for 4-8 h.
10. The method for preparing the desulfurization adsorbent for blast furnace gas according to claim 6, characterized in that the solid product is calcined at 500-550 ℃ for 4-6 hours in an air atmosphere.
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