CN103962096B - Remove the preparation method of the adsorbent of indoor low concentration hydrogen sulphide - Google Patents
Remove the preparation method of the adsorbent of indoor low concentration hydrogen sulphide Download PDFInfo
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Abstract
The present invention is to provide a kind of preparation method removing the adsorbent of indoor low concentration hydrogen sulphide.Under room temperature, 5A molecular sieve is ground to Powdered, adds in hydrochloric acid solution and soak, be then adjusted to neutrality; Be that the ammoniacal liquor of 25wt% joins in the deionized water of 300-400ml by 27g concentration, add 5-10g softex kw, Keep agitation obtains mixed liquor, then the 5A molecular sieve of activated for 8-12g process is joined in mixed liquor, stir 15min, more dropwise add 30g ethyl orthosilicate, then constant temperature stirs 1h, through suction filtration, washing, drying, roasting obtains modification 5A molecular sieve carrier; Be carried on by zinc nitrate on described modification 5A molecular sieve carrier, roasting obtains the chemosorbent that ZnO is carried on modification 5A molecular sieve.The adsorbent that the present invention obtains, it has larger specific area, flourishing pore structure, and adsorbance is large, with low cost, is easy to widely use.Be used for removing low concentration H
2s gas, is particularly suitable for removing of hydrogen sulfide gas in the confined space such as indoor, cabin body.
Description
Technical field
That the present invention relates to is a kind of preparation method of hydrogen sulfide adsorbent, and specifically one is used for removing low concentration H
2the preparation method of the hydrogen sulfide adsorbent of S gas.
Background technology
Hydrogen sulfide is a kind of high excitant toxic gas with rotten egg smell, is one of major pollutants of air.It is corroding metal material not only, but also pollutes the environment, and is detrimental to health.Therefore, various countries have all carried out strict control to the discharge standard of hydrogen sulfide, and China specifies that the concentration of emission of hydrogen sulfide must not be greater than 0.01mg/m
3, the removal of the removal of hydrogen sulfide particularly low concentration hydrogen sulphide is the problem needing solution badly.In recent years, a large amount of research work has been carried out in the removal research of Chinese scholars to low concentration hydrogen sulphide.H containing low concentration in air in airtight indoor and cabin
2s gas, needs a kind of adsorbent to remove process to it.Active carbon has larger specific area due to it, and absorption property is ideal, is widely used in the process of gas.But because it mainly relies on physical absorption, when environment changes, its adsorption effect can change, and desorption effect is not fairly obvious, the pernicious gas of confined space well can not be eliminated.
5A molecular sieve is one of a kind of the most frequently used air separation adsorbent.Because it has flourishing pore structure and larger specific area, and the advantage such as acidproof, alkaline-resisting, cheap, be suitable for the desulfurization of indoor and cabin body.5A molecular sieve generally belongs to physical absorption to the absorption of the sulfurous gas such as hydrogen sulfide, desorption can occur under certain condition.Metal oxide easily and hydrogen sulfide react and desulfurization, but metal oxide need make loose structure, and has certain intensity.By metal oxide supported in 5A molecular sieve surface, the object of desulfurization can be reached.
Summary of the invention
The object of the present invention is to provide and a kind ofly have larger specific area, flourishing pore structure, adsorbance is large, with low cost, is easy to the widely used preparation method removing indoor low concentration hydrogen sulphide adsorbent.
The object of the present invention is achieved like this:
(1) 5A molecular sieve activation process: be ground to Powdered by 5A molecular sieve under room temperature, adds in hydrochloric acid solution, and magnetic agitation soaks 3 hours, then adds Na
2cO
3solution makes mixed liquor be neutral;
(2) modification of 5A molecular sieve: be that the ammoniacal liquor of 25wt% joins in the deionized water of 300-400ml by 27g concentration, 23-27 DEG C of temperature constant magnetic stirring 15min, slowly add 5-10g softex kw, Keep agitation 15min obtains mixed liquor, then the 5A molecular sieve of activated for 8-12g process is slowly joined in described mixed liquor, continue constant temperature and stir 15min, dropwise add 30g ethyl orthosilicate again, then constant temperature stirs 1h, through suction filtration, washing, drying, roasting obtains modification 5A molecular sieve carrier;
(3) be carried on by zinc nitrate on described modification 5A molecular sieve carrier, roasting obtains the chemosorbent that ZnO is carried on modification 5A molecular sieve.
The described 30g ethyl orthosilicate that dropwise adds completes within the 20-30min time.
The sintering temperature of roasting described in the modifying process of 5A molecular sieve is 550 DEG C.
Zinc nitrate be carried on modification 5A molecular sieve carrier after the sintering temperature of roasting be 400-450 DEG C.
Described being carried on by zinc nitrate described modification 5A molecular sieve carrier refers to be carried on prepared modification 5A molecular sieve carrier by ZnO10wt%, 20wt%, 30wt%, 40wt%.
The invention provides a kind of modification 5A molecular sieve is the adsorbent of carrier, has larger specific area, flourishing pore structure, and adsorbance is large, with low cost, is easy to widely use.Be used for removing low concentration H
2s gas, is particularly suitable for removing of hydrogen sulfide gas in the confined space such as indoor, cabin body.
Zinc oxide is carried on the 5A molecular sieve surface of modification by the present invention, plays the object of chemisorbed.
5A molecular sieve is a kind of porous material, by CaONa
2oAl
2o
3siO
2deng composition, add a certain amount of acid, the various impurity in structure pore can be discharged, play and certain open up hole effect, specific area is strengthened further, and adsorption effect increases.
The present invention's tool compared with chemosorbent of the same type has the following advantages.(1) adsorbance is large: because zinc oxide of the present invention/modification 5A molecular sieve adsorbent has larger specific area, has skin effect and makes zinc oxide can be good at being carried on modification 5A molecular sieve surface.Zinc oxide and H
2s gas generation chemical reaction, plays good chemisorbed effect.(2) energy-saving material-saving: what utilize due to this invention is all the material of market at prices relative moderate.And due to its excellent adsorption, remove H
2s performance is good.Make the consumption of adsorbent adsorbent amount relatively of the same type few, material-saving successful.
Accompanying drawing explanation
Fig. 1 is that the chemosorbent load different content ZnO when 298K utilizing the present invention to prepare adsorbs H
2the breakthrough curve comparison diagram of S gas.
Fig. 2 is the chemosorbent load 30wt%ZnO absorption H under different sintering temperature when 298K utilizing the present invention to prepare
2the breakthrough curve comparison diagram of S gas.
Detailed description of the invention
Technical scheme of the present invention mainly comprises the steps:
The preparation method of the molecular sieve carried zinc oxide chemosorbent of modification 5A comprises the steps:
(1) 5A molecular sieve activation process: be ground to Powdered by 5A molecular sieve at 25 DEG C, adds in hydrochloric acid solution, and magnetic agitation soaks 3 hours, then adds Na
2cO
3solution makes mixed liquor be neutral.
More specifically, described activation method comprises the following steps: at room temperature 5A molecular sieve (spherical) is ground to powder, is joined in the hydrochloric acid of 2mol/L, mix and blend 3h activation process.By 1mol/L Na
2cO
3solution adds in the hydrochloric acid solution containing molecular sieve to neutralization.After put into air dry oven 105 DEG C of dry 24h and obtain desciccate, be ground to Powdered and obtain powder with 200 mesh standard sieves screenings, stand-by.
(2) modification of 5A molecular sieve: take 27g ammoniacal liquor (25wt%) and join in the deionized water of 300-400ml, 23-27 DEG C of temperature constant magnetic stirring 15min.After take 5-10g CTMAB (softex kw) and slowly join in solution, Keep agitation 15min.Then 5A molecular sieve (8-12g) complete for drying is slowly joined in mixed liquor, continue constant temperature and stir 15min.Molecular sieve is mixed.Take 30g ethyl orthosilicate (TEOS) and dropwise join (20-30min) in the mixed liquor of stirring.Then constant temperature stirs 1h.By mixed liquor through suction filtration, washing, drying.Roasting obtains modification 5A molecular sieve carrier (sintering temperature is 550 DEG C).
(3) zinc nitrate is carried on prepared carrier by ZnO10wt%, 20wt%, 30wt%, 40wt%.Roasting in Muffle furnace (sintering temperature is 400-450 DEG C) obtains the chemosorbent that different content ZnO is carried on modification 5A molecular sieve.
The invention will be further described below.
Embodiment 1
At 25 DEG C, 5A molecular sieve (spherical) is ground to powder, is joined in the hydrochloric acid of 2mol/L, mixing magnetic agitation 3h activation process.After add Na
2cO
3solution is to neutralization.Then sample is put into air dry oven 105 DEG C of dry 12h and obtain desciccate, be ground to Powdered and obtain powder with 200 mesh standard sieve screenings, stand-by.
The preparation of modification 5A molecular sieve carrier: take 27g ammoniacal liquor and join in the deionized water of 300-400ml, 23-27 DEG C of constant temperature stirs 15min.After take 5-10g CTMAB and slowly join in solution, Keep agitation 15min.Then 5A molecular sieve (8-12g) complete for drying is slowly joined in mixed liquor, continue constant temperature and stir 15min.Molecular sieve is mixed.Take 30g TEOS and dropwise join (20-30min) in the mixed liquor of stirring.Then constant temperature stirs 1h.By mixed liquor through suction filtration, washing, drying.The modification 5A molecular sieve carrier (sintering temperature adopts temperature programming, 25-300 DEG C (30min), 300 DEG C (30min), 300-550 DEG C (30min) 550 DEG C (300min)) of roasting.Then the sample after roasting is placed on roasting in Muffle furnace (sintering temperature is 400-450 DEG C) and obtains modification 5A molecular sieve carrier.
Embodiment 2
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO10wt%.Roasting in Muffle furnace (sintering temperature is 400-450 DEG C) obtains the modification 5A molecular sieve adsorbent that load has 10wt%ZnO.
Embodiment 3
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared 5A molecular sieve carrier by ZnO20wt%.Roasting in Muffle furnace (sintering temperature is 400-450 DEG C) obtains the modification 5A molecular sieve adsorbent that load has 20wt%ZnO.
Embodiment 4
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO30wt%.Roasting in Muffle furnace (sintering temperature is 400-450 DEG C) obtains the modification 5A molecular sieve adsorbent that load has 30wt%ZnO.
Embodiment 5
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO40wt%.Roasting in Muffle furnace (sintering temperature is 400 DEG C) obtains the modification 5A molecular sieve adsorbent that load has 40wt%ZnO.
Embodiment 6
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO30wt%.It is the modification 5A molecular sieve adsorbent that the load of 200 DEG C has 30wt%ZnO that roasting in Muffle furnace (sintering temperature is 200 DEG C) obtains sintering temperature.
Embodiment 7
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by zinc oxide 30wt%.It is the modification 5A molecular sieve adsorbent that the load of 300 DEG C has 30wt% zinc oxide that roasting in Muffle furnace (sintering temperature is 300 DEG C) obtains sintering temperature.
Embodiment 8
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO30wt%.It is the modification 5A molecular sieve adsorbent that the load of 400 DEG C has 30wt%ZnO that roasting in Muffle furnace (sintering temperature is 400 DEG C) obtains sintering temperature.
Embodiment 9
Preparation 5A molecular sieve carrier as described in Example 1.Zinc nitrate is carried on prepared carrier by ZnO30wt%.It is the modification 5A molecular sieve adsorbent that the load of 250 DEG C has 30wt%ZnO that roasting in Muffle furnace (sintering temperature is 250 DEG C) obtains sintering temperature.
H is carried out to the sorbent material prepared by above-described embodiment 1-5
2the breakthrough experiment of S gas measures.Fig. 1 is that (inlet gas concentration is 145ppm for the breakthrough curve of chemosorbent 25 DEG C time of the ZnO loaded modified 5A molecular sieve gained of different content.0.5g adsorbent, flow velocity 150ml/min), the chemosorbent adopting the present invention to prepare as seen from Figure 1 has very high absorption property, and better with the chemosorbent absorption property prepared by embodiment 4, and time of break-through is the longest.Fig. 2 shows the adsorbent breakthrough experiment curve 25 DEG C time of employing prepared by different sintering temperature, and (inlet gas concentration is 125ppm.0.5g adsorbent, flow velocity 150ml/min), can find out, the time of break-through when sintering temperature is 250 DEG C is the longest, and the adsorption effect of chemosorbent is best.
In sum, the chemosorbent time of break-through of the high absorption property utilizing the present invention to prepare is long, is obviously better than adsorbent of the same type on market.
Claims (5)
1. remove a preparation method for the adsorbent of indoor low concentration hydrogen sulphide, it is characterized in that:
(1) 5A molecular sieve activation process: be ground to Powdered by 5A molecular sieve under room temperature, adds in hydrochloric acid solution, and magnetic agitation soaks 3 hours, then adds Na
2cO
3solution makes mixed liquor be neutral;
(2) modification of 5A molecular sieve: be that the ammoniacal liquor of 25wt% joins in the deionized water of 300-400ml by 27g concentration, 23-27 DEG C of temperature constant magnetic stirring 15min, slowly add 5-10g softex kw, Keep agitation 15min obtains mixed liquor, then the 5A molecular sieve of activated for 8-12g process is slowly joined in described mixed liquor, continue constant temperature and stir 15min, dropwise add 30g ethyl orthosilicate again, then constant temperature stirs 1h, through suction filtration, washing, drying, roasting obtains modification 5A molecular sieve carrier;
(3) zinc nitrate is carried on described modification 5A molecular sieve carrier, roasting obtains the chemosorbent that ZnO is carried on modification 5A molecular sieve, and described being carried on by zinc nitrate described modification 5A molecular sieve carrier refers to be carried on prepared modification 5A molecular sieve carrier by ZnO10wt%, 20wt%, 30wt%, 40wt%.
2. the preparation method removing the adsorbent of indoor low concentration hydrogen sulphide according to claim 1, is characterized in that: the described 30g ethyl orthosilicate that dropwise adds completes within the 20-30min time.
3. the preparation method removing the adsorbent of indoor low concentration hydrogen sulphide according to claim 1 and 2, is characterized in that: the sintering temperature of roasting described in the modifying process of 5A molecular sieve is 550 DEG C.
4. the preparation method removing the adsorbent of indoor low concentration hydrogen sulphide according to claim 1 and 2, is characterized in that: zinc nitrate be carried on modification 5A molecular sieve carrier after the sintering temperature of roasting be 400-450 DEG C.
5. the preparation method removing the adsorbent of indoor low concentration hydrogen sulphide according to claim 3, is characterized in that: zinc nitrate be carried on modification 5A molecular sieve carrier after the sintering temperature of roasting be 400-450 DEG C.
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Cited By (1)
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| CN109569498A (en) * | 2018-12-26 | 2019-04-05 | 西安元创化工科技股份有限公司 | A kind of preparation method of renewable hydrogen sulfide gas adsorbent |
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| CN105344338A (en) * | 2015-12-08 | 2016-02-24 | 无锡拓能自动化科技有限公司 | Preparation method of hydrogen sulfide gas adsorbing agent |
| CN108554368A (en) * | 2018-04-25 | 2018-09-21 | 福州大学 | A kind of preparation method and application of the adsorbent of removing low concentration hydrogen sulphide |
| CN108837797A (en) * | 2018-06-26 | 2018-11-20 | 李金磊 | A kind of adsorbent and preparation method thereof for separating benzothiophene |
| CN108837796A (en) * | 2018-06-26 | 2018-11-20 | 李金磊 | It is a kind of for separating the desulfurizing agent and preparation method thereof of 2,5- thioxene |
| CN110180316A (en) * | 2019-06-10 | 2019-08-30 | 哈尔滨理工大学 | Zinc modified molecular sieve type deodorant preparation method |
| CN116440856A (en) * | 2023-01-19 | 2023-07-18 | 清华大学 | Hydrogen sulfide removing adsorbent and preparation method thereof |
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