CN109289771A - The preparation method of high-efficiency mercury removal adsorbent - Google Patents
The preparation method of high-efficiency mercury removal adsorbent Download PDFInfo
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- CN109289771A CN109289771A CN201811242581.4A CN201811242581A CN109289771A CN 109289771 A CN109289771 A CN 109289771A CN 201811242581 A CN201811242581 A CN 201811242581A CN 109289771 A CN109289771 A CN 109289771A
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- mercury removal
- removal adsorbent
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
Abstract
The invention discloses a kind of preparation methods of high-efficiency mercury removal adsorbent, based on resin balls, successively through swelling, sulfonation, washing, charing and activation, obtain rich in porous spherical Carbon Materials；Most high-efficiency mercury removal adsorbent is formed through ammonium chloride dipping and heat treatment afterwards.Raw material sources of the present invention are extensive, simple process is controllable, operating condition is mild, and the demercuration rate of gained high-efficiency mercury removal adsorbent at different temperatures is up to 75% or more.
Description
Technical field
The invention belongs to the preparation technical field of demercuration material, specially a kind of preparation method of high-efficiency mercury removal adsorbent.
Background technique
Carbon Materials are widely used in laboratory because its raw material is extensive, absorption property is excellent, method of modifying is varied
In research and actual condition, there is the ability of trapping nonvalent mercury well in coal-fired flue-gas.But come from existing result of study
It sees, the disadvantages such as the generally existing oxidation activity of the Carbon Materials reported at present is low, demercuration efficiency is low.
The presence of halogen (chlorine, bromine etc.) can promote the oxidation of the mercury of carbon surface, be conducive to the easy adsorption reaction object in surface, to mercury
Absorption and oxidation are very significant.Therefore, it is improved by table phase Modified Activated Carbon material load chlorine on existing Research foundation
Oxidation susceptibility has very important significance to exploitation high-efficiency mercury removal with adsorbent.
Summary of the invention
That it is an object of the present invention to provide a kind of simple processes is controllable, operating condition is mild, demercuration method preparation of good performance
High-efficiency mercury removal adsorbent.
The present invention is achieved by the following technical scheme:
A kind of preparation method of high-efficiency mercury removal adsorbent, includes the following steps,
(1), resin balls and dichloroethanes are added in three-necked flask with the mass ratio of 2:3, then in 80 DEG C and 300 ~ 500r/
It is uniformly mixed under min mixing speed；
(2), 150 ~ 300mL sulfuric acid is added in above-mentioned solution, continues to be stirred and heated to 160 DEG C of 6 ~ 10h of reaction, is cooled to
After room temperature, sulfate resin ball is obtained by filtration；
(3), the resulting sulfate resin ball of step (2) is added in the dilute sulfuric acid that concentration is 50% ~ 80% and is washed, then use deionization
It is washed to neutrality, obtains pretreatment resin balls；
(4), the resulting pretreatment resin balls of step (3) are risen into 500 ~ 700 DEG C of constant temperature charings by room temperature in high temperature process furnances
Then temperature is risen to 800 ~ 900 DEG C by 1.5 ~ 3h, be passed through 40 ~ 80mL/min vapor constant temperature and activate 1 ~ 3h, be naturally cooling to room
Temperature is obtained rich in porous spherical Carbon Materials；
(5), by the resulting spherical Carbon Materials of step (4), chloride and deionized water with 20 ~ 40:35 ~ 55:40 ~ 65 mass ratio
It is added in three-necked flask, while reaction system is stirred at room temperature 15 ~ for 24 hours, reaction solution is filtered after reaction, vacuum is dry
It is dried overnight spare for 95 ~ 110 DEG C in dry case, obtains pre-processing spherical Carbon Materials；
(6), the spherical Carbon Materials of the resulting pretreatment of step (5) are added in high temperature process furnances and 350 ~ 450 DEG C of heat is risen to by room temperature
1 ~ 2.5h is handled, high-efficiency mercury removal adsorbent is obtained.
In above-mentioned preparation method, the resin balls are weak-base ion-exchange resin ball or strong basic ion exchange resin ball
One or two kinds of mixtures.
In above-mentioned preparation method, sulfuric acid described in step (2) is 98% concentrated sulfuric acid.
In above-mentioned preparation method, chloride described in step (5) is ammonium chloride or potassium chloride.
Beneficial effects of the present invention are as follows:
The preparation method of high-efficiency mercury removal adsorbent provided by the invention, simple process is controllable, operating condition is mild, specific resin balls
Based on, successively through swelling, sulfonation, washing, charing and activation, obtain rich in porous spherical Carbon Materials；Most afterwards through ammonium chloride
Dipping and heat treatment form high-efficiency mercury removal adsorbent.The demercuration rate of gained high-efficiency mercury removal adsorbent at different temperatures up to 75% with
On.
Detailed description of the invention
Fig. 1 shows the SEM figures of high-efficiency mercury removal adsorbent prepared by embodiment 1.
Fig. 2 indicates the SEM figure of high-efficiency mercury removal adsorbent prepared by embodiment 2.
Fig. 3 indicates the SEM figure of high-efficiency mercury removal adsorbent prepared by embodiment 3.
Fig. 4 indicates the demercuration application under 4 different temperatures of embodiment and the demercuration curve graph under comparative example 1,2 different temperatures.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
The preparation method of high-efficiency mercury removal adsorbent of the present invention, based on resin balls, successively through swelling, sulfonation,
Washing, charing and activation, obtain rich in porous spherical Carbon Materials；Most high-efficiency mercury removal is formed through ammonium chloride dipping and heat treatment afterwards
Adsorbent.Raw material sources of the present invention are extensive, simple process is controllable, operating condition is mild, and gained high-efficiency mercury removal adsorbent is in difference
At a temperature of demercuration rate up to 75% or more.
Specific embodiment is as follows:
Embodiment 1
A kind of preparation method of high-efficiency mercury removal adsorbent, includes the following steps:
(1), 100g strong basic ion exchange resin ball and 150g dichloroethanes are added in three-necked flask, then at 80 DEG C and
It is uniformly mixed under 300r/min mixing speed；
(2), the 150mL concentrated sulfuric acid is added in above-mentioned solution, continues to be stirred and heated to 160 DEG C of reaction 6h, is cooled to room temperature
Afterwards, sulfate resin ball is obtained by filtration；
(3), above-mentioned sulfate resin ball is added in the dilute sulfuric acid that concentration is 50% and is washed, then be washed with deionized water to neutrality,
Obtain pretreatment resin balls；
(4), above-mentioned pretreatment resin balls are risen into 500 DEG C of constant temperature charing 1.5h by room temperature in high temperature process furnances, it then will be warm
Degree rises to 800 DEG C, is passed through 40mL/min vapor constant temperature activation 1h, is naturally cooling to room temperature and obtains rich in porous spherical raw material of wood-charcoal
Material；
(5), the spherical Carbon Materials of 40g, 70g chloride and 80g deionized water are added in three-necked flask, while reaction system is existed
15 h are stirred at room temperature, after reaction filter reaction solution, are dried overnight spare for 95 DEG C in vacuum oven, are pre-processed
Spherical Carbon Materials；
(6), above-mentioned pretreatment spherical shape Carbon Materials are added in high temperature process furnances and 350 DEG C of heat treatment 1h is risen to by room temperature, obtain height
Imitate demercuration adsorbent.
Fig. 1 shows the SEM figure of the high-efficiency mercury removal adsorbent of the preparation of embodiment 1.
Embodiment 2
A kind of preparation method of high-efficiency mercury removal adsorbent, includes the following steps:
(1), 120g weak-base ion-exchange resin ball and 180g dichloroethanes are added in three-necked flask, then at 80 DEG C and
It is uniformly mixed under 400r/min mixing speed；
(2), the 250mL concentrated sulfuric acid is added in above-mentioned solution, continues to be stirred and heated to 160 DEG C of reaction 8h, is cooled to room temperature
Afterwards, sulfate resin ball is obtained by filtration；
(3), above-mentioned sulfate resin ball is added in the dilute sulfuric acid that concentration is 70% and is washed, then be washed with deionized water to neutrality,
Obtain pretreatment resin balls；
(4), above-mentioned pretreatment resin balls are risen into 600 DEG C of constant temperature charing 2.5h by room temperature in high temperature process furnances, it then will be warm
Degree rises to 850 DEG C, is passed through 60mL/min vapor constant temperature activation 2h, is naturally cooling to room temperature and obtains rich in porous spherical raw material of wood-charcoal
Material；
(5), the spherical Carbon Materials of 60g, 90g chloride and 110g deionized water are added in three-necked flask, while by reaction system
20h is stirred at room temperature, after reaction filters reaction solution, is dried overnight spare for 100 DEG C in vacuum oven, obtains pre- place
Manage spherical Carbon Materials；
(6), above-mentioned pretreatment spherical shape Carbon Materials are added in high temperature process furnances and 400 DEG C of heat treatment 1.5h is risen to by room temperature, obtained
High-efficiency mercury removal adsorbent.
Fig. 2 shows the SEM figures of high-efficiency mercury removal adsorbent prepared by embodiment 2.
Embodiment 3
A kind of preparation method of high-efficiency mercury removal adsorbent, includes the following steps:
(1), 140g strong basic ion exchange resin ball and 210g dichloroethanes are added in three-necked flask, then at 80 DEG C and
It is uniformly mixed under 500r/min mixing speed；
(2), the 300mL concentrated sulfuric acid is added in above-mentioned solution, continues to be stirred and heated to 160 DEG C of reaction 10h, is cooled to room
Sulfate resin ball is obtained by filtration in Wen Hou；
(3), above-mentioned sulfate resin ball is added in the dilute sulfuric acid that concentration is 80% and is washed, then be washed with deionized water to neutrality, obtained
To pretreatment resin balls；
(4), above-mentioned pretreatment resin balls are risen into 700 DEG C of constant temperature charing 3h by room temperature in high temperature process furnances, then by temperature
900 DEG C are risen to, 80mL/min vapor constant temperature activation 3h is passed through, is naturally cooling to room temperature and obtains rich in porous spherical raw material of wood-charcoal
Material；
(5), the spherical Carbon Materials of 80g, 110g chloride and 130g deionized water are added in three-necked flask, while by reaction system
It is stirred at room temperature for 24 hours, after reaction filters reaction solution, be dried overnight spare for 110 DEG C in vacuum oven, obtain pre- place
Manage spherical Carbon Materials；
(6), above-mentioned pretreatment spherical shape Carbon Materials are added in high temperature process furnances and 450 DEG C of heat treatment 2.5h is risen to by room temperature, obtained
High-efficiency mercury removal adsorbent.
Fig. 3 shows the SEM figure of the high-efficiency mercury removal adsorbent of the preparation of embodiment 3.
The high-efficiency mercury removal adsorbent of 1,2,3 preparations through the embodiment of the present invention is obtained high it can be seen from Fig. 1,2,3
It is flourishing to imitate demercuration adsorbent hole.
Embodiment 4
The high-efficiency mercury removal adsorbent of 1,2,3 preparations tests the demercuration performance under different temperatures respectively through the embodiment of the present invention.
Specific experiment condition is: demercuration reaction carries out on the atmospheric fixed bed reactor that internal diameter is 15mm.Test mould
Quasi- flue gas composition are as follows: the concentration of mercury is 0.50 ± 0.05mg/m3, N2With the O of 4vol.%2For carrier gas, temperature operating ranges 50-
200 DEG C, the modified demercuration sorbing material of flue gas flow 600mL/min, 35mg silver, air speed 8000h-1.The double light of outlet mercury concentration
Digital display mercury analyzer (SG-921, Jiangfen Ltd.) carries out on-line real-time measuremen.
Comparative example 1
Using the demercuration performance passed through under the spherical carbon testing of materials different temperatures that steam activation obtains in embodiment 1, specifically
Experiment condition it is consistent with the experiment condition in embodiment 4.
Comparative example 2
Using the demercuration performance passed through under the spherical carbon testing of materials different temperatures that steam activation obtains in embodiment 2, specifically
Experiment condition it is consistent with the experiment condition in embodiment 4.
Measure the demercuration performance under sample 1,2,3 and comparative example 1,2 different temperatures respectively by on-line real-time measuremen,
Specifically as shown in figure 4, being directlyed adopt the de- of the spherical Carbon Materials obtained in embodiment 1 and embodiment 3 by steam activation
Mercury rate is lower, and passes through the demercuration rate of high-efficiency mercury removal adsorbent prepared by embodiment 1,2,3 up to 75% or more
It should be pointed out that without departing from the principle of the present invention, may be used also for the those skilled in the art of the art
To make several improvement and application, these are improved and application is also considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of high-efficiency mercury removal adsorbent, characterized by the following steps:
(1), resin balls and dichloroethanes are added in three-necked flask with the mass ratio of 2:3, then 80 DEG C and 300 ~
It is uniformly mixed under 500r/min mixing speed；
(2), sulfuric acid is added in above-mentioned solution, continues to be stirred and heated to 160 DEG C of 6 ~ 10h of reaction, after being cooled to room temperature, mistake
Filter obtains sulfate resin ball；
(3), the resulting sulfate resin ball of step (2) is added in the dilute sulfuric acid that concentration is 50% ~ 80% and is washed, then use deionization
It is washed to neutrality, obtains pretreatment resin balls；
(4), the resulting pretreatment resin balls of step (3) are risen into 500 ~ 700 DEG C of constant temperature charings by room temperature in high temperature process furnances
Then temperature is risen to 800 ~ 900 DEG C by 1.5 ~ 3h, be passed through 40 ~ 80mL/min vapor constant temperature and activate 1 ~ 3h, be naturally cooling to room
Temperature is obtained rich in porous spherical Carbon Materials；
(5), by the resulting spherical Carbon Materials of step (4), chloride and deionized water with 20 ~ 40:35 ~ 55:40 ~ 65 mass ratio
It is added in three-necked flask, while reaction system is stirred at room temperature 15 ~ for 24 hours, reaction solution is filtered after reaction, vacuum is dry
It is dried overnight spare for 95 ~ 110 DEG C in dry case, obtains pre-processing spherical Carbon Materials；
(6), the spherical Carbon Materials of the resulting pretreatment of step (5) are added in high temperature process furnances and 350 ~ 450 DEG C of heat is risen to by room temperature
1 ~ 2.5h is handled, high-efficiency mercury removal adsorbent is obtained.
2. the preparation method of high-efficiency mercury removal adsorbent according to claim 1, it is characterised in that: the resin balls are weak base
One or two kinds of mixtures of property ion exchange resin ball or strong basic ion exchange resin ball.
3. the preparation method of high-efficiency mercury removal adsorbent according to claim 1, it is characterised in that: in step (2), the sulphur
Acid is 98% concentrated sulfuric acid.
4. the preparation method of high-efficiency mercury removal adsorbent according to claim 1, it is characterised in that: in step (5), the chlorine
Compound is ammonium chloride or potassium chloride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110479208A (en) * | 2019-07-26 | 2019-11-22 | 天津浩创节能环保设备有限公司 | A kind of preparation and regeneration method of efficient carbon-based demercuration adsorbent |
| CN114029031A (en) * | 2021-09-26 | 2022-02-11 | 北京清新环境技术股份有限公司 | Composition for preparing demercuration adsorbent, demercuration adsorbent and preparation method thereof |
| CN114620721A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of weakly basic ion exchange resin-based carbon beads |
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| CN1480397A (en) * | 2003-07-18 | 2004-03-10 | 中国科学院山西煤炭化学研究所 | Method for preparing spherical active cardon with base of highstrength resin |
| MX2017014741A (en) * | 2015-05-27 | 2018-03-23 | Lubrizol Corp | Aggregating compositions, modified particulate solid compositions, and methods for making and using same. |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110479208A (en) * | 2019-07-26 | 2019-11-22 | 天津浩创节能环保设备有限公司 | A kind of preparation and regeneration method of efficient carbon-based demercuration adsorbent |
| CN114620721A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of weakly basic ion exchange resin-based carbon beads |
| CN114029031A (en) * | 2021-09-26 | 2022-02-11 | 北京清新环境技术股份有限公司 | Composition for preparing demercuration adsorbent, demercuration adsorbent and preparation method thereof |
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