CN101934221B - Modified adsorbent and preparation method thereof - Google Patents
Modified adsorbent and preparation method thereof Download PDFInfo
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- CN101934221B CN101934221B CN201010508426A CN201010508426A CN101934221B CN 101934221 B CN101934221 B CN 101934221B CN 201010508426 A CN201010508426 A CN 201010508426A CN 201010508426 A CN201010508426 A CN 201010508426A CN 101934221 B CN101934221 B CN 101934221B
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Abstract
The invention provides a modified adsorbent and a preparation method thereof, which relate to active carbon. The modified adsorbent comprises the following raw materials in a mass ratio: 16-20 of active carbon and 1 of benzoic acid. The preparation method comprises the following steps of: putting bar-shaped active carbon in a water bath; washing grease, ash content and alkaline oxygen-containing functional groups in the active carbon away from the surface of the active carbon; grinding the washed active carbon after being dried; putting the ground active carbon into a solution dissolved with the benzoic acid after being calcined, and shaking the active carbon into a constant-temperature cultivation shaking bed to obtain a solution containing the benzoic acid and the active carbon; and filtering the solution containing the benzoic acid and the active carbon to obtain an active carbon filter cake, and drying the active carbon filter cake to obtain the modified active carbon after. The invention adopts the oxygen-containing functional groups capable of increasing the HgO absorption capacity of the active carbon, successfully loads the oxygen-containing functional groups on the surface of the active carbon and greatly increases the HgO absorption capacity of the active carbon. A test shows that the absorption capacity of the chemically-modified active carbon is obviously increased.
Description
Technical field
The present invention relates to a kind of active carbon, especially relate to a kind of modified adsorbent and preparation method thereof.
Background technology
The proposition of mercury pollution control problem is in 1999 the earliest in the coal-burning power plant, is pointed out by Environmental Protection Agency: 1149 boilers in 64 power plant in the U.S. whole nation discharge 43 tons of mercury in atmosphere; Environmental Protection Agency was also made requirement effectively decision of the discharging of control mercury in 2007 in 2000.And there are some researches show; If do not take effectively to control the measure of mercury pollution to the year two thousand twenty whole world; The human health loss that is then caused by methyl mercury can surpass 3,700,000,000 dollars (the dollar value of money with 2005 calculates), and is opposite, if take measures to make the discharge capacity of mercury to reduce to 50%～60%; To the year two thousand twenty, the whole world can obtain 18～2,200,000,000 dollar benefit.China is the use big country of coal.2004; The coal consumption of China is 1,400,000,000 tons; And the coal consumption amount in North America and Europe is 10.5 hundred million tons and 400,000,000 tons; And the mercury emissions problem of coal-burning power plant and received the great attention of China unlike oxysulfide and nitrogen oxide, government does not take measures such as corresponding environmental protection, government decree to control effectively the discharging of Hg yet.Therefore the mercury pollution problem that is produced by the coal-burning power plant is at China's very outstanding that seem.
The data that Environmental Protection Agency provides show that the mercury that emits in the coal-burning power plant is mainly with Hg
0Form be main because the Hg that exists with compound or particulate form form
2+Can in cleaner or wet desulphurization device, effectively be removed, yet these environmental protection equipments are for Hg
0Removal effect not high.At present, remove Hg
0Effective method be that active carbon injects absorption method, this be because:
1, the huge specific area of active carbon provides material base for the absorption pollutant;
2, this method is simple and easy to do, is applicable to most power plant;
3, there is not secondary pollution in this method.
But; Injection method in the utilization of U.S. power plant need active carbon be 10000: 1 with the use amount that C/Hg calculates; This price that not only means every degree electricity will go up 0.1～0.8 cent; And the use amount of active carbon is equivalent to the content of the flying dust that 1%～2% coal combustion discharges in injection method, if active carbon surpasses 1% in the ratio of flying dust, can influence the price of flying dust as concrete substitute so.In order to reduce the use cost of active carbon injection method, improve active carbon to Hg
0Adsorption capacity become the certain feasible important channel of improving injection method.
The raising active carbon of report is to Hg at present
0The method of adsorption capacity mainly can be divided into two big types:
1, inorganic modified method is like carried by active carbon S, Cl, I or MnCl
2
2, organically-modified method, mainly there are some important oxygen-containing functional groups in this based on activated carbon surface.These oxygen-containing functional groups are to Hg
0Be absorbed with significant effects.Someone works out and utilizes HNO
3, H
2O
2, O
3Or the free hydroxyl of electrolysis generation etc. ([1] is virgin new, Wang Junhui, and free state mercury is deviate from the oxidation modification charcoal absorption. Chinese environmental protection industry, 2007 (12): p.52-54; [2] Y.H.Li, C.W.Lee, B.K.Gullett, Importance of activated carbon ' s oxygen surface functional groups on elemental mercury adsorption.Fuel, 2003.82:451-457; [3] P.Chingombe, B.Saha, R.J.wakeman, surface modification and characterisation of a coal-based activated carbon.Carbon, 2005.43:3132-3143)
The strong oxidizer magnesium oxide/absorbent charcoal increases the surface oxygen functional group content of active carbon greatly, and these methods may improve active carbon to Hg
0Adsorption capacity, still, these methods have also all increased the content of the multiple oxygen-containing functional group of activated carbon surface bar none, and the increase of some oxygen-containing functional group content can suppress the absorption of mercury, suppress active carbon to Hg like the increase of hydroxyl
0Absorption (mistake! Do not find Reference source.Luo Jinying, Luo Jinjing, the preparation of modified activated carbon and to the absorption of gaseous mercury research. the plain technology of charcoal, 2009).
But in " improve the preparation of active carbon and to the absorption research of gaseous mercury ", the author has only inquired into preliminary preparation method, lacks load capacity that how to obtain best oxygen-containing functional group and the important method that quantitative study goes out this load content.
Summary of the invention
The objective of the invention is in order effectively to improve active carbon Hg in the flue
0Removal, a kind of modified adsorbent and preparation method thereof is provided.
The raw material of modified adsorbent according to the invention is formed and is active carbon by the content of mass ratio: benzoic acid is (16～20): 1, and active carbon preferably: benzoic acid is 20: 1.
The preparation method of modified adsorbent according to the invention may further comprise the steps:
1) with bar-shaped active carbon through water-bath, the grease in the active carbon and ash content and alkaline oxygen-containing functional group are washed from activated carbon surface;
In step 1), the temperature of said water-bath can be 100 ℃, and the time of water-bath can be 10min, preferably repeatedly 3 times.
2) after the active carbon drying after will washing, grind;
In step 2) in, said drying can be placed on the active carbon after the washing 106 ℃ of dryings in the drying box, said grinding, and sealed sample preparation disintegrating machine capable of using grinds between active carbon to 100～200 orders.
3) after the calcining of the active carbon after will grinding, place to be dissolved with benzoic solution, and in the constant temperature culture shaking table, shake, must contain the solution of benzoic acid and active carbon;
In step 3), said calcining can be with active carbon at N
21000 ℃ of calcinings of high temperature in the atmosphere, N
2Flow velocity can be 0.3～0.4L/min and keep 2h, be cooled to normal temperature then; Said concussion can be shaken under the condition of 25 ℃ of 125rpm.
The solution that 4) will contain benzoic acid and active carbon filters, and obtains the active carbon filter cake, promptly obtains modified activated carbon after the drying.
In step 4), said drying can be dry under 106 ℃ in drying box with the active carbon filter cake.
Compare with existing modified activated carbon, the outstanding advantage of modified activated carbon according to the invention is:
In list of references [4], modified activated carbon is under the condition identical with this experiment, and saturated extent of adsorption is 20 μ g/g; The present invention is on the basis of list of references [4]; Found and promoted the optimum load benzoic acid content that nonvalent mercury absorbs; And detect the optimum load amount of load oxygen-containing functional group through experiment, therefore the saturated extent of adsorption of modified activated carbon of the present invention is 100～200 μ g/g.
For obtaining more oxygen-containing functional group, modifying method of activated carbon commonly used has:
1) strong oxidizing process, the red fuming nitric acid (RFNA) that utilizes 6mol/L is with the active carbon oxidation, because red fuming nitric acid (RFNA) has very strong corrosivity, the raffinate of preparation can be brought the secondary pollution problem; The present invention is in 20: 1 proportionings of active carbon and benzoic acid, and the raffinate concentration of benzoic acid solution has only 1/100 of initial soln.
2) in electrochemical method; Activated carbon surface produces more than a kind of oxygen-containing functional group; But multiple oxygen-containing functional group produces simultaneously, and the existence meeting of some functional group is restricted and make electrochemical oxidation process prepare Application of Brand Active Carbon because suppress the absorption of active carbon to nonvalent mercury.
The present invention adopts can improve active carbon to Hg
0The oxygen-containing functional group of absorptive capacity, and this kind oxygen-containing functional group successfully loaded on the activated carbon surface, active carbon improved greatly to Hg
0Adsorption capacity.Test shows that the adsorption capacity of the active carbon of process chemical modification significantly improves.
Description of drawings
Fig. 1 is the adsorption effect experimental rig sketch map of modified activated carbon according to the invention.In Fig. 1, respectively be labeled as 1, nitrogen cylinder; 2,3,12～16, quartzy valve; 4,5, mass flow controller; 6, vent cabinet; 7, bead; 8, digital control constant temperature tank; 9, mercury osmos tube; 10, U type quartz ampoule; 11, blender (preheater); 17, tube furnace; 18, active carbon adsorption column; 19, temperature controller; 20, mercury vapourmeter; 21, afterbody active carbon adsorption column.
Fig. 2 is the saturated extent of adsorption of the modified activated carbon of different loads carboxyl-content of the present invention to nonvalent mercury.In Fig. 2, abscissa is carboxyl load content mmol/g, and ordinate is saturated extent of adsorption μ g/g.
The specific embodiment
Following examples will combine accompanying drawing that the present invention is further described.
1) gets bar-shaped active carbon 100g, heat 100 ℃ to seething with excitement and keeping 10min, 3 times repeatedly with 1g C/16.66mL water; Bar-shaped active carbon through water-bath, is washed the grease in the active carbon and ash content and alkaline oxygen-containing functional group get off from activated carbon surface;
2) active carbon after will washing is placed in the drying box 106 ℃ of dry 4h to constant weight; Grind active carbon 10min with the sealed sample preparation disintegrating machine of GJ-1 type, particle diameter finally is ground to 100～200 orders;
3) after the calcining of the active carbon after will grinding, place to be dissolved with benzoic solution, and in the constant temperature culture shaking table, shake, must contain the solution of benzoic acid and active carbon; Said calcining can be with active carbon at N
21000 ℃ of calcinings of high temperature in the atmosphere, N
2Flow velocity can be 0.3～0.4L/min and keep 2h, be cooled to normal temperature then; Said concussion can be shaken under the condition of 25 ℃ of 125rpm.
4) take out active carbon, the 0.4200g active carbon is added volume in the vacuum glove box of CSX-1 type be in the benzoic acid solution of 150mL, and wherein the preparation method of load benzoic acid solution is: 0.0700g benzoic acid (AR) is dissolved in the 500mL deionized water; The benzoic acid solution that contains active carbon in the constant temperature culture shaking table with concussion 24h under the state of 25 ℃ of 125rpm.
5) concussion finishes, and with vacuum filtration device filtering solution, obtains filter cake, again filter cake is put into drying box, with 106.5 ℃ of dry 4h, obtains modified activated carbon.
Below provide the adsorption effect and the analysis of causes of the prepared modified activated carbon of the present invention.
(as shown in Figure 1) carries out adsorption experiment in the simulation gas circuit, to check modified activated carbon and unmodified active carbon to Hg
0Adsorption effect, Hg wherein
0Entrance concentration is 10 μ g/m
3, this is the mercurous concentration of China coal-burning power plant flue gas standard.
Experimental result:
Unmodified active carbon is to Hg
0Adsorption capacity be: 26 μ g/g.
Active carbon after the modification is to Hg
0Adsorption capacity be: 100～200 μ g/g.
The cause of increased of the adsorption capacity after the modification carboxyl that has been load, carboxyl can effectively promote active carbon to Hg
0Chemisorbed, through laboratory facilities, detect the carboxyl-content 0.0229mmol/g of the active carbon before unmodified, the carboxyl-content after the modification is 0.138mmol/g.But the benzoic content of load is different, and saturated extent of adsorption is also different: when load content is 0.0793mmol/g, saturated extent of adsorption is 69.63 μ g/g; Load content is 0.21mmol/g, and saturated extent of adsorption is 24.8 μ g/g; Load content is 0.432mmol/g, and saturated extent of adsorption is 6.375 μ g/g.
The physical parameter of active carbon and benzoic physical property are referring to table 1 and 2.
Table 1
Table 2
Claims (6)
1. the preparation method of a modified adsorbent, the raw material that it is characterized in that said modified adsorbent is formed and is active carbon by the content of mass ratio: benzoic acid is 16～20: 1;
Said preparation method may further comprise the steps:
1) with bar-shaped active carbon through water-bath, the grease in the active carbon and ash content and alkaline oxygen-containing functional group are washed from activated carbon surface; The temperature of said water-bath is 100 ℃, and the time of water-bath is 10min;
2) after the active carbon drying after will washing, grind;
3) after the calcining of the active carbon after will grinding, place to be dissolved with benzoic solution, and in the constant temperature culture shaking table, shake, must contain the solution of benzoic acid and active carbon; Said calcining is at N with active carbon
21000 ℃ of calcinings of high temperature are cooled to normal temperature then in the atmosphere; Said concussion is under the condition of 25 ℃ of 125rpm, to shake; Said N
2Flow velocity be 0.3～0.4L/min and keep 2h;
The solution that 4) will contain benzoic acid and active carbon filters, and obtains the active carbon filter cake, promptly obtains modified activated carbon after the drying.
2. the preparation method of a kind of modified adsorbent as claimed in claim 1 is characterized in that its raw material is formed and is active carbon by the content of mass ratio: benzoic acid is 20: 1.
3. the preparation method of a kind of modified adsorbent as claimed in claim 1 is characterized in that in step 1), said water-bath 3 times repeatedly.
4. the preparation method of a kind of modified adsorbent as claimed in claim 1 is characterized in that in step 2) in, said drying is that the active carbon after the washing is placed on 106 ℃ of dryings in the drying box.
5. the preparation method of a kind of modified adsorbent as claimed in claim 1 is characterized in that in step 2) in, said grinding is to utilize sealed sample pulverizer to grind between active carbon to 100～200 orders.
6. the preparation method of a kind of modified adsorbent as claimed in claim 1 is characterized in that in step 4), and said drying is dry under 106 ℃ in drying box with the active carbon filter cake.
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| CN102557923A (en) * | 2011-12-02 | 2012-07-11 | 江苏远洋药业股份有限公司 | Method for purifying benzoyl chloride reaction terminating solution |
| CN102513061B (en) * | 2011-12-29 | 2013-06-19 | 翟云波 | Modified active carbon and preparation method and application thereof |
| CN102698724B (en) * | 2012-04-06 | 2014-11-05 | 淮北市大华活性炭有限公司 | Method for producing active carbon for gasoline vapor adsorption |
| CN103468046B (en) * | 2013-08-23 | 2015-02-11 | 洛阳好生活环保科技有限公司 | Activated carbon finishing paint |
| CN105136602B (en) * | 2015-09-07 | 2020-08-04 | 宁夏出入境检验检疫局检验检疫综合技术中心 | Activated carbon comprehensive gas adsorption instrument |
| CN105688808A (en) * | 2016-01-21 | 2016-06-22 | 广西大学 | Mixing type grease adsorbent |
| CN105920037B (en) * | 2016-06-20 | 2019-01-22 | 贵州泰柏妇科疾病研究中心 | A kind of application of active carbon nanoparticles colloidal sol in preparation treatment herpesvirus medicament |
| CN106732351B (en) * | 2016-11-22 | 2019-08-06 | 新奥生态环境治理有限公司 | A kind of modified activated carbon and preparation method thereof |
| CN108126654A (en) * | 2017-12-08 | 2018-06-08 | 北京东方计量测试研究所 | A kind of material for air purification, preparation method and application |
| CN111530413B (en) * | 2020-04-15 | 2022-09-02 | 广东省微生物研究所（广东省微生物分析检测中心） | Biochar for enhancing soil self-repair and preparation method and application thereof |
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| CN101695651B (en) * | 2009-10-27 | 2012-07-04 | 昆明理工大学 | Copper and iron-loaded modified activated carbon absorbent and method for preparing same |
| CN101791537A (en) * | 2010-02-11 | 2010-08-04 | 天津城市建设学院 | Modified sludge activated carbon used for low-concentration flue gas desulfurization and denitration and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 罗锦英等."改性活性炭吸附气态汞的试验研究".《中国电机工程学报》.2009,第29卷(第35期),第78页左栏第3段、1.1.1、1.1.2，第79页2.1、表1，第80页2.5，第81页图7. |
| 罗锦英等."改性活性炭吸附气态汞的试验研究".《中国电机工程学报》.2009,第29卷(第35期),第78页左栏第3段、1.1.1、1.1.2,第79页2.1、表1,第80页2.5,第81页图7. * |
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Effective date of registration: 20191128 Address after: 363105 nantaiwu high tech Industrial Zone, Gangwei Town, Longhai City, Zhangzhou City, Fujian Province Patentee after: Xingang Thermal Engineering (Zhangzhou) Co., Ltd Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: Xiamen University |
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