CN101492162B - Modified active coke, production and uses thereof - Google Patents
Modified active coke, production and uses thereof Download PDFInfo
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- CN101492162B CN101492162B CN2009100794611A CN200910079461A CN101492162B CN 101492162 B CN101492162 B CN 101492162B CN 2009100794611 A CN2009100794611 A CN 2009100794611A CN 200910079461 A CN200910079461 A CN 200910079461A CN 101492162 B CN101492162 B CN 101492162B
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- activated coke
- coke
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- correcting agent
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Abstract
The invention discloses modified activated coke, and a preparation method and application thereof. The modified activated coke provided by the invention is the activated coke loaded with a modifier, and the modifier is at least one of bromide salt, bromate, iodate, chloride salt, and chlorate. The modified activated coke has strong capacity of adsorbing mercury, and has the demercuration efficiency in flue gas more than 95 percent. The invention utilizes the prior coal resources at home to prepare the modified activated coke with high performance, low cost and simple process, and achieves ideal effect when used for the demercuration in the flue gas. The invention contributes to solving the problems that the prior active carbon has high manufacturing cost and the prior activated coke has low demercuration efficiency, and has great economic value and social significance.
Description
Technical field
The present invention relates to a kind of modified active coke and its production and application.
Background technology
In recent years, because the enhancing day by day of home and abroad environment protection cry, all contaminations that fired coal combustion is produced is controlled becomes a problem demanding prompt solution.Contain the trace heavy metals element mercury in the coal, in combustion processes, be easy to evaporate and be discharged in the atmosphere with flue gas, and it can exist for a long time in atmosphere, reach can polluted source after a certain amount of when it settles down, cause that the fish mercury content exceeds standard, the transmission by food chain makes people's health take in a large amount of mercury elements then, has a strong impact on people's physical function and health, therefore, each state emission standard in working out flue gas all.
It is a lot of to utilize various sorbent materials to remove the research of simple substance mercury in the flue gas, and the most general technology of industrialized utilization is the pulverized powder activated carbon method at present.Gac is used for removing the mercury of flue gas as a kind of sorbent material, and cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of modified active coke and its production and application.
Modified active coke provided by the invention is to handle the modified active coke that activated coke obtains with properties-correcting agent; Described properties-correcting agent is at least a in Bromide, bromate, iodized salt, iodate, chlorate and the oxymuriate.
Describedly handle activated coke with properties-correcting agent and specifically can under 150-300 ℃ temperature, carry out.
The described modifier solution processing activated coke of handling the concrete available 0.1%-10% of activated coke (quality percentage composition) with properties-correcting agent.Described modifier solution specifically can be the aqueous solution of properties-correcting agent.
Described processing specifically can be spraying and handles.
Described activated coke can adopt commercially available activated coke, also can adopt homemade activated coke.Can prepare activated coke with the following method: 1) hard coal fragmentation, abrasive dust kneading, press strip are shaped, dry; 2) product with step 1) carries out charing, obtains carbonizing production, and the charing finishing temperature is 550-700 ℃, and carbonization time is 0.5-2 hour; 3) carbonizing production is activated, activation temperature is 700-950 ℃, and soak time is 0.5-2 hour, obtains activated coke.
Described modified active coke has the vesicular structure of activated coke, and the active sites of carrying out producing after modification is handled with properties-correcting agent has improved its mercury adsorptive power.
The present invention also provides a kind of preparation method of modified active coke, comprises the step of handling activated coke with properties-correcting agent; Described properties-correcting agent is at least a in Bromide, bromate, iodized salt, iodate, chlorate and the oxymuriate.
Describedly handle activated coke with properties-correcting agent and specifically can under 150-300 ℃ temperature, carry out.
The described modifier solution processing activated coke of handling the concrete available 0.1%-10% of activated coke (quality percentage composition) with properties-correcting agent.Described modifier solution specifically can be the aqueous solution of properties-correcting agent.
Described processing specifically can be spraying and handles.
Described activated coke can adopt commercially available activated coke, also can adopt homemade activated coke.Can prepare activated coke with the following method: 1) hard coal fragmentation, abrasive dust kneading, press strip are shaped, dry; 2) product with step 1) carries out charing, obtains carbonizing production, and the charing finishing temperature is 550-700 ℃, and carbonization time is 0.5-2 hour; 3) carbonizing production is activated, activation temperature is 700-950 ℃, and soak time is 0.5-2 hour, obtains activated coke.
Described modified active coke can be applicable to adsorptive gaseous mercury.
Described modified active coke can be applicable at fume mercury-removing (flue gas demercuration).
Adopt modified active coke of the present invention to carry out flue gas demercuration, compare with existing gac and have the following advantages:
(1) preparation technology.The activation degree of activated coke is less than the gac height, so the output of activated coke unit product is higher, activation temperature is relatively low, and is more energy-conservation.Reaction parameter in activated coke and the process for preparing active carbon sees Table 1.
Reaction parameter in table 1 activated coke and the process for preparing active carbon
(2) process application advantage.Physical strength specific activity Jiao of gac is low, so easier fragmentation in industrial application.The cost specific activity of gac is burnt high, and there is limitation in large-scale industrial application.
(3) the removing of mercury in the flue gas.The demercuration efficient performance of modified active coke is not weaker than modified activated carbon, and reason is as follows: unmodified activated coke removes mercury mainly based on physical adsorption, and removal efficiency is not high, and average about 30%; Behind various modifier modifications, the removal efficiency of modified active coke can reach more than 95%, and this is based on chemisorption because of modification activated coke demercuration later; Therefore, though the specific surface area of activated coke (is generally 200-400m
2/ g) be lower than gac (500-600m
2More than/the g), be main sorbent material still for chemisorption, only require certain specific surface area, the major influence factors that how much is only removal efficiency of active sites.
The invention provides a kind of modified active coke.Modified active coke of the present invention has the ability of extremely strong absorption mercury, and demercuration efficient reaches more than 95% in flue gas.Modified active coke of the present invention has high-performance, low cost, the simple advantage of preparation technology simultaneously.The present invention utilizes domestic existing coal resources to prepare high-performance, low cost, the simple modified active coke of technology, is used for flue gas processing demercuration and reaches more satisfactory effect.The present invention helps to solve existing gac cost height, and the present situation of activated coke demercuration inefficiency has great economic worth and social effect.
Description of drawings
Fig. 1 is operational path Fig. 1 of preparation activated coke.
Fig. 2 is the structural representation of modified active coke preparation facilities.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is to buy from routine biochemistry reagent shop and obtains.
The preparation of embodiment 1, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 0.1% Potassium Bromide (KBr) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 550 ℃, and the time is 2 hours, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 800 ℃, and the time is 1 hour, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.Device shown in Figure 2 is a top-down closed system, comprises fog nozzle (1), right import (2), left import (3), heating zone (4), feed opening (5) and body of heater (6).During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 150 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The preparation of embodiment 2, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 10% potassium bromate (KBrO
3) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 700 ℃, and the time is 1 hour, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 950 ℃, and the time is 0.5 hour, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 300 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The preparation of embodiment 3, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 1% potassiumiodide (KI) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 700 ℃, and the time is 0.5 hour, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 850 ℃, and the time is 1.5 hours, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 200 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The preparation of embodiment 4, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 5% Potassium Iodate (KIO
3) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 600 ℃, and the time is 2 hours, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 800 ℃, and the time is 1 hour, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 250 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The preparation of embodiment 5, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 7% Repone K (KCl) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 550 ℃, and the time is 2 hours, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 850 ℃, and the time is 1 hour, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 200 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The preparation of embodiment 6, modified active coke
One, the preparation of properties-correcting agent
Preparation quality percentage composition is 1% Potcrate (KClO
3) aqueous solution.
Two, the preparation of activated coke
Operational path is as shown in Figure 1, and is specific as follows:
1, with the hard coal fragmentation, carry out abrasive dust then and mediate, press strip is shaped, and dries stand-by.
2, the product with step 1 carries out charing, and finishing temperature is 650 ℃, and the time is 1.5 hours, obtains carbonizing production.
3, the carbonizing production with step 2 activates, and temperature is 700 ℃, and the time is 2 hours, obtains activated coke.
Three, the preparation of modified active coke
Adopt the coating legal system to be equipped with modified active coke.Prepare modified active coke with device shown in Figure 2.During use, (the body of heater stage casing is to hypomere) heats in the heating zone, and Heating temperature is 200 ℃.
The activated coke that step 2 prepares is imported by the right import (2) and the left import (3) at top, carry out the spraying (modifier solution of step 1 preparation) of properties-correcting agent simultaneously at the top by fog nozzle (1), impel activated coke fully to contact with properties-correcting agent, activated coke utilizes the effect of gravity can enter the bottom, activated coke is dropped in the process of bottom by the middle part, because system is under the hot state, oven dry rapidly, feed opening (5) is arranged in the bottom, directly the material of bottom is emitted, obtain modified active coke.
The performance measurement of embodiment 7, modified active coke
The modified active coke that embodiment 1 to embodiment 6 is prepared carries out performance measurement, and method is as follows:
Adopt the simulated flue gas component gas to estimate the demercuration performance of activated coke, promptly feed N
2, O
2, water vapour, CO
2, SO
2And mercury vapour.Part N
2Mercury vapour is taken out of by the mercury permeation tube as carrier gas, entered the absorption reaction device then.Total gas couette is 1000ml/min, wherein N
2Gas flow as carrier gas is 400ml/min, O
2Account for 6% (volumn concentration) of total gas couette, water vapour accounts for 10% (volumn concentration) of total gas couette, CO
2Account for 10% (volumn concentration) of total gas couette, SO
2Account for 0.2% (volumn concentration) of total gas couette, remain into nitrogen as balance gas.The adsorption temp that evaluation experimental adopts is 140 ℃, and adsorber is fixed-bed reactor, and the modified active coke consumption of loading is 500mg, and the mercury concentration of feeding is 50 μ g/m
3Absorption gas later enters the mercury vapor analyzer proofing unit, judges the performance of activated coke demercuration according to the change in concentration result of mercury before and after the absorption.The mercury vapor analyzer proofing unit is the fluorescence mercury vapor analyzer (SUZHOUQING peace Instr Ltd., QM201-H type fluorescence mercury vapor analyzer) of gold amalgam principle, when measuring, enters preceding must the placement of instrument 10%SnCl is housed
2The reducing apparatus of solution (quality percentage composition), purpose are in order to reduce the mercury of oxidation state in the adsorber exit gas.Experimental result utilizes demercuration efficient to characterize, and demercuration efficient is meant the ratio of the difference of Reactor inlet mercury concentration and reactor outlet mercury concentration with import mercury concentration, and its expression formula is:
η＝(n
0-n
1)/n
0×100％
In the formula: η is a removal efficiency; n
0Be import mercury concentration, μ g/m
3n
1Be outlet mercury concentration, μ g/m
3
Each test is provided with three repetitions, results averaged.The performance measurement of the modified active coke that embodiment 1 to embodiment 6 prepares the results are shown in Table 2.
The demercuration efficient of the modified active coke that table 2 embodiment 1 to embodiment 6 prepares
The result shows that the modified active coke that obtains with the present invention carries out flue gas demercuration, and removal efficiency all reaches more than 95%.
Claims (4)
1. a modified active coke is to handle the modified active coke that activated coke obtains with properties-correcting agent; Described properties-correcting agent is at least a in Bromide, bromate, iodized salt, iodate, chlorate and the oxymuriate;
Described is to carry out under 150-300 ℃ temperature with properties-correcting agent processing activated coke;
Described is to handle activated coke with the modifier solution of 0.1%-10% (quality percentage composition) with properties-correcting agent processing activated coke; Describedly be treated to spraying and handle;
The preparation method of described activated coke comprises the steps: 1) hard coal fragmentation, abrasive dust kneading, press strip are shaped, dry; 2) product with step 1) carries out charing, obtains carbonizing production, and the charing finishing temperature is 550-700 ℃, and carbonization time is 0.5-2 hour; 3) carbonizing production is activated, activation temperature is 700-950 ℃, and soak time is 0.5-2 hour, obtains activated coke.
2. the preparation method of modified active coke comprises the step of handling activated coke with properties-correcting agent; Described properties-correcting agent is at least a in Bromide, bromate, iodized salt, iodate, chlorate and the oxymuriate;
Described is to carry out under 150-300 ℃ temperature with properties-correcting agent processing activated coke;
Described is to handle activated coke with the modifier solution of 0.1%-10% (quality percentage composition) with properties-correcting agent processing activated coke; Describedly be treated to spraying and handle;
The preparation method of described activated coke comprises the steps: 1) hard coal fragmentation, abrasive dust kneading, press strip are shaped, dry; 2) product with step 1) carries out charing, obtains carbonizing production, and the charing finishing temperature is 550-700 ℃, and carbonization time is 0.5-2 hour; 3) carbonizing production is activated, activation temperature is 700-950 ℃, and soak time is 0.5-2 hour, obtains activated coke.
3. the application of the described modified active coke of claim 1 in adsorptive gaseous mercury.
4. the application of the described modified active coke of claim 1 in fume mercury-removing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100794611A CN101492162B (en) | 2009-03-11 | 2009-03-11 | Modified active coke, production and uses thereof |
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|---|---|---|---|
| CN2009100794611A CN101492162B (en) | 2009-03-11 | 2009-03-11 | Modified active coke, production and uses thereof |
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| CN101492162B true CN101492162B (en) | 2011-02-02 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985099B (en) * | 2010-11-22 | 2013-11-20 | 东南大学 | Flue gas demercuration adsorbent and preparation method thereof |
| CN103894151B (en) * | 2014-04-16 | 2016-05-11 | 北京建筑大学 | A kind of activated coke method of modifying and for removing the application process of recycled water heavy metal |
| CN104276569B (en) * | 2014-10-21 | 2016-01-27 | 中国科学院山西煤炭化学研究所 | A kind of method improving asphalt-base globular active carbon crushing strength |
| CN110404505B (en) * | 2018-04-27 | 2021-06-08 | 中国矿业大学(北京) | Preparation method of activated carbon for measuring gaseous mercury and activated carbon |
| CN109174140B (en) * | 2018-09-10 | 2021-05-25 | 太原科技大学 | Flue gas desulfurization and demercuration catalyst and preparation method and application thereof |
| CN109806839B (en) * | 2019-03-29 | 2022-01-28 | 平罗县国宁活性炭有限公司 | Preparation method of active coke |
| CN112642413A (en) * | 2020-12-10 | 2021-04-13 | 北京清新环境技术股份有限公司 | Preparation method and product of mercury removal adsorbent based on active coke |
| CN113663641A (en) * | 2021-08-24 | 2021-11-19 | 航天环境工程有限公司 | Preparation method and application of novel mercury removal 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 |
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