CN101829541A - Mesoporous molecular sieve base nano metallic oxide and preparation method of desulfurizer thereof - Google Patents
Mesoporous molecular sieve base nano metallic oxide and preparation method of desulfurizer thereof Download PDFInfo
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- CN101829541A CN101829541A CN 201010195134 CN201010195134A CN101829541A CN 101829541 A CN101829541 A CN 101829541A CN 201010195134 CN201010195134 CN 201010195134 CN 201010195134 A CN201010195134 A CN 201010195134A CN 101829541 A CN101829541 A CN 101829541A
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- desulfurizing agent
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Abstract
The invention discloses a mesoporous molecular sieve base nano metallic oxide and a preparation method of a desulfurizer thereof, belonging to the technical field of chemical industry. The nano metallic oxide is one of ferric oxide, copper oxide and zinc oxide, and the mesoporous molecular sieve is MCM-41, and bore diameter ranges from 2 to 10 nm. The preparation method comprises the following steps: 1, dissolving metallic nitrate into 50 ml of absolute ethyl alcohol, and oscillating for 30 min; 2, adding 1 g of a mesoporous molecular sieve material, and continuing oscillating for 30 min; 3, after ultrasonic treatment, adopting a centrifugal machine to dewater; 4, after the sample is dried at room temperature for 2 d, putting the sample into an oven to be dried; and 5, putting the dried sample into a muffle furnace to be roasted, and finally shaping to prepare granular desulfurizer.
Description
Technical field
That the present invention relates to is a kind of preparation method of oxide and desulfurizing agent thereof of chemical technology field, the preparation method of particularly a kind of mesoporous molecular sieve base nano metallic oxide and desulfurizing agent thereof.
Background technology
Hydrogen sulfide is the extremely strong poisonous gas of harmfulness, and the health that not only seriously threatens the people also can cause degradation problem under chemical industry equipment and corrosion of piping thereof, catalyst poisoning and the product quality, therefore must control its pollution.At present, using wider sulfur method mainly is bioanalysis and chemical method, and bioanalysis is fit to handle low concentration low-speed sulfurous gas, and desulfurization precision is low.Chemical method desulfurization precision height can be handled high concentration high-speed sulfurous gas.Chemical method is divided into wet method and dry method two big classes again: wet method mainly contains iron-based (Lo-Cat method, Sulferox method, Konox method) and two kinds of processes of vanadium base (improvement ADA method, tannin extract method, OMC method, KCA and Tea Polyphenols method); What dry-desulphurizer mainly used is active carbon and metal oxide.In general, the wet desulphurization method has the advantage that operating cost is low, disposal ability is big, but the equipment investment height, technology is complicated; Dry desulfurization has the precision height, and technology is simple, the advantage of convenient operating maintenance.
Iron oxide and zinc oxide are the metal oxide desulfurizers of using always, and they rely on the pore structure that forms in the manufacture process and come adsorption of hydrogen sulfide, and the chemical reaction of desulfurization takes place then.Owing to be difficult to form abundant microporous in these preparation of metal oxides processes, cause a large amount of metal oxide bodies can not participate in reaction, so this class desulfurizing agent preparation cost be often higher; Secondly, because this class desulfurizing agent specific area is little, cause desulfuration efficiency lower, its disposable Sulfur capacity is not higher than 200mg H usually
2S/g absorbent, the air speed of handling gas is not higher than 5000h
-1The 3rd, such desulfurizing agent is formed by more active preparation of metal oxides, and is active higher, easily causes desulfurizing agent bed temperature height, produces the temperature runaway phenomenon, finally causes desulfurizing agent bed sintering, makes sweetening process control difficulty strengthen.Cupric oxide is the moderate metal oxide of a kind of activity, is difficult for producing the temperature runaway phenomenon in the sweetening process.Cupric oxide is difficult for forming loose structure, is difficult to directly make desulfurizing agent but on the one hand; On the other hand, because itself is active, be difficult to satisfy industrial requirements with cupric oxide as reactive desulfurizing agent speed merely.
Mesoporous material has nano level duct or cage and the modifiable inner surface that order is arranged, assemble or finishing by the physical chemistry means, introduce the object that some has specific function, can improve the performance of mesoporous material itself greatly, form excellent functional mesoporous material.The nano particle that deposits the high degree of dispersion with catalytic activity on mesoporous material is an important and effective method of Catalyst Design.Because the granular of particle size, specific area sharply increases, and makes nano particle produce small-size effect, skin effect, even quantum size effect, macro quanta tunnel effect.Realize metallic compound fixing on mesoporous material, can take following method: directly at mesoporous inner surface grafting metallo-organic compound; Behind mesoporous inner surface grafting silanization molecule, the functional group on the organic group is carried out functionalization, metallic compound is combined in the functional group; Synthetic and the fixing metal compound in mesopore orbit by ion-exchange or electrostatic attraction method.Compare with this several method, ultrasonic wave assistant soakage method has that operating process is simple, dipping effect is stable, the advantages such as preparation of good reproducibility, suitable high capacity amount metallic catalyst as a result.
By retrieval, do not find the metal oxide-loaded report that is used for the gas hydrogen sulfide removal on mesoporous material as yet.
Summary of the invention
The present invention is directed to the deficiency of existing metal oxide desulfur technology, a kind of preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent is provided.This method is utilized the ultrasonic wave assistant soakage, and the metal nitrate that ethanol is dissolved penetrates in the duct of mesopore molecular sieve equably, then by high-temperature roasting, makes the novel mesopore molecular sieve desulfurizing agent that load has reactive metal oxides.Compare with conventional metals oxide desulfurizing agent, novel desulfurizing agent has steadily advantages such as (no temperature runaway phenomenon produce) of desulphurization reaction fast (can handle the high-speed dusty gas), good, the disposable Sulfur capacity height of desulfurization precision and desulphurization reaction process.This desulfurizing agent is suitable for handling the dusty gas of atm number under the industrial condition, high-speed, high hydrogen sulfide content, especially when treatment conditions require desulfurization precision height and reaction normal temperature.Also can be used for the removal of hydrogen sulfide in coal gas, synthesis gas and the chemical emission.
The present invention is achieved by the following scheme:
The present invention relates to a kind of mesoporous molecular sieve base nano metallic oxide, a kind of in iron oxide, cupric oxide and the zinc oxide;
Described mesopore molecular sieve is MCM-41, and pore diameter range is 2～10nm.
The present invention relates to the desulfurizing agent preparation method of above-mentioned mesoporous molecular sieve base nano metallic oxide, comprise the steps:
Step 1 takes by weighing 0.2～3g metal nitrate, is dissolved in the 50ml absolute ethyl alcohol, vibration 30min;
Step 2 adds the 1g meso-porous molecular sieve material, continues vibration 30min;
Step 3, ultrasonic wave are managed the back outward and are used centrifuge dewatering;
Step 4, sample is placed in the baking oven dry at drying at room temperature 2d.
Step 5, drying sample place the Muffle furnace roasting, and granular desulfurizing agent is made in last moulding.
Metal nitrate described in the step 1 is a kind of in ferric nitrate, copper nitrate, the zinc nitrate.
Ultrasonic wave described in the step 3 is handled, and is meant the alcohol mixeding liquid of containing metal nitrate and mesoporous material is put into the ultrasonic oscillator oscillation treatment, and to improve dipping effect, the processing time is 10～30min.Described centrifugal, be meant the alcohol mixeding liquid of containing metal nitrate and mesoporous material is put into centrifuge centrifugal dehydration 20～40min that rotating speed is 2000～4000rpm/min.
Oven drying described in the step 4 is meant dry 10～15h under the temperature of 353K;
Muffle furnace roasting described in the step 5, the roasting temperature 3～5h that is meant at 523～723K.Described granular, be meant that the desulfurizing agent of gained is broken into pieces behind the compressing tablet in tablet press machine, make the particle between 60～80 orders.
The mesoporous molecular sieve base nano metallic oxide desulfurizing agent that the present invention proposes, it is desulphurizing activated by using penetration capacity assay method as described below to assess.Get the novel desulfurizing agent of 100mg and fill in (long 40mm in the glass tube, diameter 2mm), about desulfurizing agent packed height 25mm, in gas mixing bottle, cooperate the back to feed desulfurizing agent layer in the glass tube column hydrogen sulfide gas with air, the air inlet concentration of hydrogen sulfide is 5000ppm, and air speed is 75000～150000h
-1, when exit concentration reaches 50ppm, off-test.
The specific embodiment
The following example 1～3 is being to implement under the prerequisite with the technical solution of the present invention, provided detailed enforcement design and result, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Take by weighing the 3g ferric nitrate and be dissolved in the 50ml absolute ethyl alcohol, add 1g mesoporous material MCM-41 behind the vibration 30min, continue vibration 30min.Place ultrasonic oscillator to handle 20min said mixture.After dipping was finished, mixture was put into centrifuge (2000rpm/min) centrifugal dehydration 40min, takes off a layer sediment, place air drying after 2 days, put into baking oven, in Muffle furnace, carry out roasting then in the dry 10h of 353K, sintering temperature is 723K, and roasting time is 3h.At last make granular meso-porous desulfurizer through overmolding.The desulfurizing agent that said method is made, its specific area are 368m
2/ g, total pore volume are 0.419cm
3/ g.When air speed is 150000h
-1, when the outlet concentration of hydrogen sulfide reached 50ppm, the disposable Sulfur capacity of prepared mesoporous molecular sieve base nano ferric oxide desulfurizer reached 476mg H
2S/g absorbent.Iron content improves or reduces, and a Sulfur capacity of material all reduces.
Embodiment 2
Take by weighing the 0.2g copper nitrate and be dissolved in the 50ml absolute ethyl alcohol, add 1g mesoporous material MCM-41 behind the vibration 30min, continue vibration 30min.Place ultrasonic oscillator to handle 30min said mixture.After dipping was finished, mixture was put into centrifuge (3000rpm/min) centrifugal dehydration 30min, takes off a layer sediment, place air drying after 2 days, put into baking oven, in Muffle furnace, carry out roasting then in the dry 15h of 353K, sintering temperature is 623K, and roasting time is 4h.At last make granular meso-porous desulfurizer through overmolding.The desulfurizing agent that said method is made, its specific area are 627m
2/ g, total pore volume are 0.691cm
3/ g.When air speed is 100000h
-1, when the outlet concentration of hydrogen sulfide reached 50ppm, the disposable Sulfur capacity of prepared mesoporous molecular sieve base nano cupric oxide desulfurizing agent reached 281mg H
2S/g absorbent.Copper content improves or reduces, and the disposable Sulfur capacity of material all reduces.
Embodiment 3
Take by weighing the 0.5g zinc nitrate and be dissolved in the 50ml absolute ethyl alcohol, add 1g mesoporous material MCM-41 behind the vibration 30min, continue vibration 30min.Place ultrasonic oscillator to handle 10min said mixture.After dipping was finished, mixture was put into centrifuge (4000rpm/min) centrifugal dehydration 20min, takes off a layer sediment, place air drying after 2 days, put into baking oven, in Muffle furnace, carry out roasting then in the dry 12h of 353K, sintering temperature is 523K, and roasting time is 5h.At last make granular meso-porous desulfurizer through overmolding.The desulfurizing agent that said method is made, its specific area are 602m2/g, and total pore volume is 0.617cm3/g.When air speed is 75000h-1, when the outlet concentration of hydrogen sulfide reached 50ppm, the disposable Sulfur capacity of prepared mesoporous molecular sieve base nano Zinc oxide desulfurizer reached 213mg H2S/g absorbent.The raising of zinc content or reduction, a Sulfur capacity of material all reduces.
Claims (7)
1. mesoporous molecular sieve base nano metallic oxide is characterized in that: described nano-metal-oxide is a kind of in iron oxide, cupric oxide and the zinc oxide, and described mesopore molecular sieve is MCM-41, and pore diameter range is 2～10nm.
2. the preparation method of a mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 1 is characterized in that: comprise the steps:
Step 1 takes by weighing 0.2～3g metal nitrate, is dissolved in the 50ml absolute ethyl alcohol, vibration 30min;
Step 2 adds the 1g meso-porous molecular sieve material, continues vibration 30min;
Step 3, ultrasonic wave are managed the back outward and are used centrifuge dewatering;
Step 4, sample is placed in the baking oven dry at drying at room temperature 2d;
Step 5, drying sample place the Muffle furnace roasting, and granular meso-porous desulfurizer is made in last moulding.
3. the preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 2 is characterized in that, the described metal nitrate in the step 1 is a kind of in ferric nitrate, copper nitrate, the zinc nitrate.
4. the preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 2, it is characterized in that, ultrasonic wave described in the step 3 is managed the back outward and is used centrifuge dewatering, be meant the alcohol mixeding liquid of containing metal nitrate and mesoporous material is put into the ultrasonic oscillator oscillation treatment, to improve dipping effect, the processing time is 10～30min; Then the alcohol mixeding liquid of containing metal nitrate and mesoporous material is put into centrifuge centrifugal dehydration 20～40min that rotating speed is 2000～4000rpm/min.
5. the preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 4 is characterized in that, oven drying described in the step 4 is meant dry 10～15h under the temperature of 353K.
6. the preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 2 is characterized in that, the Muffle furnace roasting described in the step 5, the roasting temperature 3～5h that is meant at 523～723K.
7. the preparation method of mesoporous molecular sieve base nano metallic oxide desulfurizing agent according to claim 2 is characterized in that, granular described in the step 5 is meant that the desulfurizing agent of gained is broken into pieces behind the compressing tablet in tablet press machine, make the particle between 60～80 orders.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260570A (en) * | 2011-06-30 | 2011-11-30 | 华北电力大学 | Mesoporous silica base molecular sieve based iron-base oxygen carrier and preparation method thereof |
| CN102897786A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN103028367A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Gas desulfurization adsorbent, preparation method thereof and desulfurization method for sulfur-containing gas |
| CN103539612A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Desulphurization method for propylene |
| CN104741075A (en) * | 2015-03-10 | 2015-07-01 | 同济大学 | Method for modifying porous material capable of effectively removing negative ions in air |
| CN105032436A (en) * | 2015-06-30 | 2015-11-11 | 新地能源工程技术有限公司 | Super fine desulfurization agent and preparation method thereof |
| CN106423066A (en) * | 2016-12-06 | 2017-02-22 | 中国工程物理研究院材料研究所 | Adsorbent filler and preparation method thereof |
| CN108144318A (en) * | 2018-02-01 | 2018-06-12 | 南京英斯派工程技术有限公司 | A kind of associated gas desulphurization system |
| CN108531225A (en) * | 2018-05-09 | 2018-09-14 | 广州华科环保工程有限公司 | A kind of ceramic industry is from water gas deep desulfuration degreasing unit and technique |
| CN111662319A (en) * | 2020-07-24 | 2020-09-15 | 浙江皇马科技股份有限公司 | Preparation method of low-color 3-isocyanatopropyl trimethoxy silane |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
| CN114505088A (en) * | 2020-11-17 | 2022-05-17 | 滨州中科催化技术有限公司 | Coke oven gas desulfurization catalyst and preparation method and application thereof |
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Cited By (18)
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|---|---|---|---|---|
| CN102260570A (en) * | 2011-06-30 | 2011-11-30 | 华北电力大学 | Mesoporous silica base molecular sieve based iron-base oxygen carrier and preparation method thereof |
| CN103028367A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Gas desulfurization adsorbent, preparation method thereof and desulfurization method for sulfur-containing gas |
| CN103028367B (en) * | 2011-09-29 | 2014-12-03 | 中国石油化工股份有限公司 | Gas desulfurization adsorbent, preparation method thereof and desulfurization method for sulfur-containing gas |
| CN103539612A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Desulphurization method for propylene |
| CN103539612B (en) * | 2012-07-12 | 2015-08-12 | 中国石油化工股份有限公司 | Desulphurization method for propylene |
| CN102897786A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN102897786B (en) * | 2012-10-16 | 2014-10-15 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN104741075B (en) * | 2015-03-10 | 2017-01-11 | 同济大学 | Method for modifying porous material capable of effectively removing negative ions in air |
| CN104741075A (en) * | 2015-03-10 | 2015-07-01 | 同济大学 | Method for modifying porous material capable of effectively removing negative ions in air |
| CN105032436A (en) * | 2015-06-30 | 2015-11-11 | 新地能源工程技术有限公司 | Super fine desulfurization agent and preparation method thereof |
| CN106423066A (en) * | 2016-12-06 | 2017-02-22 | 中国工程物理研究院材料研究所 | Adsorbent filler and preparation method thereof |
| CN108144318A (en) * | 2018-02-01 | 2018-06-12 | 南京英斯派工程技术有限公司 | A kind of associated gas desulphurization system |
| CN108144318B (en) * | 2018-02-01 | 2023-12-19 | 南京佳华科技股份有限公司 | Associated gas desulfurization system |
| CN108531225A (en) * | 2018-05-09 | 2018-09-14 | 广州华科环保工程有限公司 | A kind of ceramic industry is from water gas deep desulfuration degreasing unit and technique |
| CN111662319A (en) * | 2020-07-24 | 2020-09-15 | 浙江皇马科技股份有限公司 | Preparation method of low-color 3-isocyanatopropyl trimethoxy silane |
| CN114505088A (en) * | 2020-11-17 | 2022-05-17 | 滨州中科催化技术有限公司 | Coke oven gas desulfurization catalyst and preparation method and application thereof |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
| CN112691651B (en) * | 2020-12-22 | 2023-05-05 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizing agent, desulfurizing agent and application |
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Open date: 20100915 |