CN102580674A - Method for preparing mercury removal agent by utilizing modified waste tire pyrolysis residue - Google Patents
Method for preparing mercury removal agent by utilizing modified waste tire pyrolysis residue Download PDFInfo
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- CN102580674A CN102580674A CN2012100399205A CN201210039920A CN102580674A CN 102580674 A CN102580674 A CN 102580674A CN 2012100399205 A CN2012100399205 A CN 2012100399205A CN 201210039920 A CN201210039920 A CN 201210039920A CN 102580674 A CN102580674 A CN 102580674A
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- mercury
- pyrolysis residue
- removal agent
- mercury removal
- tire pyrolysis
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Abstract
The invention discloses a method for preparing a mercury removal agent by utilizing a modified waste tire pyrolysis residue. The method comprises the following steps: (1) crushing the waste tire pyrolysis residue, wherein the particle sizes of particles are 60-200 meshes; (2) immersing hydrochloric acid or sulfuric acid water solution with the concentration of 30-60wt% into the waste tire pyrolysis residue in an isovolumetric manner, continuously stirring for 1h at room temperature, then drying for 48h at a temperature of 110 DEG C; and (3) activating the pyrolysis residue subjected to the acid immersion in a sealed furnace body in the atmosphere of nitrogen by using high-temperature vapor at a temperature of 800-1000 DEG C for 1-3h so as to obtain the mercury removal agent. The method has the advantages that: the mercury removal agent prepared by the modified pyrolysis residue enables the pyrolysis residue to become profitable, the price of the modified pyrolysis residue is lower than that of the modified active carbon, high mercury removal rate can be achieved at the same time, and the adsorption capacity of the modified pyrolysis residue for mercury is up to 800 mug/g.
Description
Technical field
The present invention relates to the flue gas demercuration technology, particularly a kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent.
Background technology
The energy resource structure of China is main with coal, and the coal consumption amount is also with sustainable growth.According to statistics, China's capacity of installed generator moderate heat Denso machine capacity accounts for more than 74% at present.Whole world anthropogenic discharge's mercury is approximately 1000-6000t/.Research shows: the Asia is maximum in the world anthropogenic discharge's mercury zone, and world's mercury emissions rate is surpassed 50%.Document thinks that coal combustion is one of source of maximum anthropogenic discharge's mercury.China is to be the country of main energy sources with coal, and fire coal becomes an environmental factor of can not ignore of mercury emissions.
Mercury in the coal-fired flue-gas has three kinds of forms: simple substance mercury (Hg
0), oxidation state mercury (Hg
2+, like HgCl
2Or HgO) and particle mercury (Hg
p).Mercury mainly exists with simple substance mercury and oxidation state mercury form in the coal-fired flue-gas, and simple substance mercury is its principal mode.At the high-temperature area of boiler, this discharges the mercuri in the coal with simple substance mercury, and at the low-temperature region at rear portion, part mercury has formed oxidation state mercury (HgCl then
2Or HgO).Because particle mercury generally is enriched in the flying dust surface, can remove most of through bag-type dust or electric precipitation.Account for the simple substance mercury of main component in the flue gas, because it has high volatile volatile, low-solubility, traditional adsorption method is limited in one's ability.Relative simple substance mercury, oxidation state mercury is adsorbed easily, and simultaneous oxidation attitude mercury has water-soluble, also can in follow-up wet desulfurization system, remove major part.And the removal of mercury technology of using in the industry of present foreign developed country is in flue, to spray active carbon powder, utilizes active carbon that mercury is adsorbed, but the active carbon spraying technique exists the charcoal consumption big, the shortcoming that cost is high.And general active carbon mainly is that physical absorption takes place to mercury, and adsorption capacity is limited.
To the modification of active carbon, many bibliographical informations are arranged both at home and abroad, the someone studies at technological oxides such as activated carbon surface load C e, Cu, Mn, has improved the adsorption capacity of active carbon to simple substance mercury, has also strengthened the ability that independent matter mercury is converted into mercury oxide simultaneously.Also there are some researches show, add inorganic salts such as CaCl at activated carbon surface
2, MgCl
2, CoCl
2, MnCl
2Form various surface chemistry groups, also be proved to be and accelerated the chemisorbed of activated carbon surface mercury.The load bromine can make active carbon that the adsorbance of simple substance mercury is significantly increased, and accelerates the rate of adsorption to simple substance mercury.But these researchs mostly launch to study based on active carbon.
The present invention proposes to utilize junked tire to carry out modification, is used for adsorbing the mercury of flue gas.Along with the fast development of automobile industry, junked tire increases in the output of China gradually.The present occupation mode of junked tire has tyre retreading, the method for prepare reclaimed rubber (rubber powder) and pyrolysis.Tyre retreading wherein can only be passed through limited number of times with preparation reclaimed rubber (rubber powder).So the pyrolysis processing junked tire obtains paying attention in recent years gradually, the junked tire pyrolysis processing can obtain fuel oil and carbon black, but the poor quality of carbon black, limited should technology further commercial Application.And the pyrolysis slag accounts for 35% of junked tire greatly, belongs to the difficult solid slag that utilizes.Except charcoal, also contain inorganic substances in the junked tire pyrolysis slag, these inorganic matters have comprised elements such as Zn, Fe and S.Can utilize the method for acid dip to go out the part inorganic substances, increase the specific area of pyrolysis slag, the part material that contains in the slag of pyrolysis simultaneously like metal oxide and S etc., is favourable for the oxidation of simple substance mercury with adsorbing.
Summary of the invention
The objective of the invention is to above-mentioned technical Analysis; A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent is provided; The mercury removal agent of this method preparation turns waste into wealth the pyrolysis slag, than having advantage on the modified activated carbon price; Simultaneously can obtain very high demercuration rate, modification pyrolysis slag reaches 800ug/g to the adsorption capacity of mercury.
Technical scheme of the present invention:
A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent comprises following operating procedure:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the hydrochloric acid or aqueous sulfuric acid equal-volume immersion junked tire pyrolysis slag of 30-60wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 800-1000 ℃, and soak time is 1-3 hour, can make mercury removal agent.
Technical Analysis of the present invention:
In the gas-solid heterogeneous catalytic reaction, gaseous material is attracted to material surface, and in general, under equal conditions, the specific area of material is big more, and its adsorption capacity is strong more.Adopt junked tire pyrolysis slag through acid dip and high-temperature water vapor activation among the present invention, purpose is to improve its specific area, strengthens the adsorption capacity to mercury.From absorption principle, at adsorbent surface, exist the principle of physical absorption and chemisorbed in addition, the interaction force of physical absorption mercury and material surface is lower, and the desorption phenomenon just takes place after the temperature that raises a little, so relatively also low spot of adsorption capacity.If but urge the sorbing material surface to contain some ions or functional group, can with adsorbed material generation chemical reaction, like this, the adsorption capacity of mercury and adsorption capacity can be improved.Why selecting junked tire pyrolysis slag is raw material, and reason is metal oxide such as Ze, the Fe etc. that contain in the junked tire pyrolysis slag, and S, and these elements are favourable to the catalytic oxidation of mercury with absorption.This patent utilizes isopyknic hydrochloric acid, vitriol lixiviation stain method to handle the pyrolysis slag, except dissolving part inorganic matter increases the specific area, also is incorporated into the Cl in the hydrochloric acid and the S element in the sulfuric acid surface of sorbing material simultaneously.These materials are favourable for the chemisorbed that improves mercury.The high-temperature water vapor activation is the specific area that further improves material.
In sum, the invention provides a kind of method, equal-volume method acid dip before this, and then the method for activation under high-temperature water vapor with modification pyrolysis slag.
Advantage of the present invention is: the mercury removal agent of the modification pyrolysis slag of preparation, and the pyrolysis slag is turned waste into wealth, than having advantage on the modified activated carbon price, can obtain very high demercuration rate simultaneously, modification pyrolysis slag reaches 800ug/g to the adsorption capacity of mercury.
The specific embodiment
Enumerate some examples of implementation below, but do not comprise all:
Embodiment 1:
A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent, step is following:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the aqueous hydrochloric acid solution equal-volume immersion junked tire pyrolysis slag of 60wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 1000 ℃, and soak time is 3 hours, can make mercury removal agent.
Testing result shows: this mercury removal agent reaches 800ug/g to the adsorption capacity of flue gas mercury in 100 ℃ flue-gas temperature.
Embodiment 2:
A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent, step is following:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the aqueous hydrochloric acid solution equal-volume immersion junked tire pyrolysis slag of 30wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 800 ℃, and soak time is 1 hour, can make mercury removal agent.
Testing result shows: this mercury removal agent reaches 600ug/g to the adsorption capacity of flue gas mercury in 200 ℃ flue-gas temperature.
Embodiment 3:
A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent, step is following:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the aqueous sulfuric acid equal-volume immersion junked tire pyrolysis slag of 60wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 1000 ℃, and soak time is 3 hours, can make mercury removal agent.
Testing result shows: this mercury removal agent reaches 760ug/g to the adsorption capacity of flue gas mercury in 100 ℃ flue-gas temperature.
Embodiment 4:
A kind of method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent, step is following:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the aqueous sulfuric acid equal-volume immersion junked tire pyrolysis slag of 30wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 800 ℃, and soak time is 1 hour, can make mercury removal agent.
Testing result shows: this mercury removal agent reaches 560ug/g to the adsorption capacity of flue gas mercury in 200 ℃ flue-gas temperature.
Claims (1)
1. method of utilizing modified waste tire pyrolysis slag to prepare mercury removal agent is characterized in that: comprise following operating procedure:
1) junked tire pyrolysis slag is pulverized, grain graininess is the 60-200 order;
2) be in the hydrochloric acid or aqueous sulfuric acid equal-volume immersion junked tire pyrolysis slag of 30-60wt% with concentration, continue under the room temperature to stir 1 hour, drier 48h under 110 ℃;
3) carry out activation through in the sealing body of heater of pyrolysis slag under nitrogen atmosphere of acid dip with high-temperature water vapor with above-mentioned, activation temperature is 800-1000 ℃, and soak time is 1-3 hour, can make mercury removal agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210039920 CN102580674B (en) | 2012-02-21 | 2012-02-21 | Method for preparing mercury removal agent by utilizing modified waste tire pyrolysis residue |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210039920 CN102580674B (en) | 2012-02-21 | 2012-02-21 | Method for preparing mercury removal agent by utilizing modified waste tire pyrolysis residue |
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| Publication Number | Publication Date |
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| CN102580674A true CN102580674A (en) | 2012-07-18 |
| CN102580674B CN102580674B (en) | 2013-08-14 |
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ID=46470228
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|---|---|---|---|
| CN 201210039920 Expired - Fee Related CN102580674B (en) | 2012-02-21 | 2012-02-21 | Method for preparing mercury removal agent by utilizing modified waste tire pyrolysis residue |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728321A (en) * | 2012-07-20 | 2012-10-17 | 哈尔滨工业大学 | Method for preparing adsorbent by using municipal sludge and waste tires |
| CN109517611A (en) * | 2018-12-11 | 2019-03-26 | 凤阳爱尔思轻合金精密成型有限公司 | A kind of autonomous superheated steam energy source conversion system of damaged tire of continuous high-efficient green |
| CN110013828A (en) * | 2019-03-19 | 2019-07-16 | 杭州电子科技大学 | A kind of preparation method of the new modified absorbent charcoal material for flue gas demercuration |
| CN114433019A (en) * | 2020-11-06 | 2022-05-06 | 中南财经政法大学 | Flue gas demercuration material taking cobalt-enriched plants as raw materials and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944581A (en) * | 2006-10-27 | 2007-04-11 | 清华大学 | Method for continuously thermal decomposing waste tire using gas burning kiln |
| CN101164876A (en) * | 2007-09-30 | 2008-04-23 | 南开大学 | Method for preparing carbon black and active carbon from waste tyre pyrolytic carbon |
-
2012
- 2012-02-21 CN CN 201210039920 patent/CN102580674B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944581A (en) * | 2006-10-27 | 2007-04-11 | 清华大学 | Method for continuously thermal decomposing waste tire using gas burning kiln |
| CN101164876A (en) * | 2007-09-30 | 2008-04-23 | 南开大学 | Method for preparing carbon black and active carbon from waste tyre pyrolytic carbon |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728321A (en) * | 2012-07-20 | 2012-10-17 | 哈尔滨工业大学 | Method for preparing adsorbent by using municipal sludge and waste tires |
| CN102728321B (en) * | 2012-07-20 | 2013-11-13 | 哈尔滨工业大学 | Method for preparing adsorbent by using municipal sludge and waste tires |
| CN109517611A (en) * | 2018-12-11 | 2019-03-26 | 凤阳爱尔思轻合金精密成型有限公司 | A kind of autonomous superheated steam energy source conversion system of damaged tire of continuous high-efficient green |
| CN110013828A (en) * | 2019-03-19 | 2019-07-16 | 杭州电子科技大学 | A kind of preparation method of the new modified absorbent charcoal material for flue gas demercuration |
| CN110013828B (en) * | 2019-03-19 | 2021-09-21 | 杭州电子科技大学 | Preparation method of modified activated carbon material for flue gas demercuration |
| CN114433019A (en) * | 2020-11-06 | 2022-05-06 | 中南财经政法大学 | Flue gas demercuration material taking cobalt-enriched plants as raw materials and preparation method thereof |
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|---|---|
| CN102580674B (en) | 2013-08-14 |
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Granted publication date: 20130814 Termination date: 20140221 |