CN1593744A - Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method - Google Patents
Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method Download PDFInfo
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- CN1593744A CN1593744A CN 200410024414 CN200410024414A CN1593744A CN 1593744 A CN1593744 A CN 1593744A CN 200410024414 CN200410024414 CN 200410024414 CN 200410024414 A CN200410024414 A CN 200410024414A CN 1593744 A CN1593744 A CN 1593744A
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Abstract
The invention relates to a kind of activated carbon basal material, a sulfur dioxide absorption agent, which manufactured by the way of medicine activation. The specificity of the invention is the steps as follows: put the material containing carbon into the water solution of chemical agent, then proceed the chemical modification with pressurization and hydro heating in high pressure reactor caldron, and finally, it can be manufactured by the way of drying activation. The medicine agents that mentioned above are: oxydol (H2O2), sulfur acid (H2SO4), nitrided hydrogen (HNO3), hydrogen fluoride (HF), sodium hydroxide (NaOH), potassium hydroxide (KOH), KMnO4 and so on. The source of the carbon basal material such as carbocoal is wide and the cost of it is low; the manufactured absorption agent can be used as the boiler fuel, and has no secondary pollution; and what mentioned above are the feature of the invention. Furthermore, the invention can be used widely for environmental protection of the stack gases desulfurization and purifying in coal-burning power station, coal fired boiler, and coal fired kiln.
Description
Technical field
The present invention relates to the preparation method of gas purification desulfurizing agent in the flue gas desulfurization environment purification protection industries such as a kind of coal-burning power plant, coal-burning boiler and coal-fired furnace, a kind of absorbent charcoal based material SO more specifically says so
2The preparation of adsorbent method.
Background technology
Coal accounts for 69% in the energy consumption structure of China.A large amount of burnings of coal make national atmosphere be coal-smoke pollution, and particularly since the eighties in last century, along with China's economy develops rapidly, the coal consumption amount increases day by day, SO
2Discharge capacity constantly increases, and causes the atmospheric environment severe contamination.According to statistics, China SO in 1985
2Discharge capacity is 1,530 ten thousand tons, and nineteen ninety-five just rises to 2,370 ten thousand tons, SO in 2000
2Discharge capacity is 2,590 ten thousand tons.Because SO
2A large amount of dischargings, cause environmental destruction, the acid rain phenomenon is serious.China's acid rain area has accounted for 40% of area at present, and national precipitation acidity on average raises 2-8 doubly, the rare Precipitation pH in the world occurs and is lower than 4 situation.Because the acid rain sedimentation is caused agricultural, forestry and material economic loss every year is up to more than 1,000 hundred million yuan (World Bank is estimated as 5,000 hundred million).So, prevent SO
2Atmosphere pollution further aggravates.Be based on national conditions, developing the flue gas desulfurization technique that adapts to different scales has become current and following interior quite over a long time main task.
According to China's strategy of sustainable development and China's Agenda 21, the beginning of this century, national SO
2Total emission volumn must not surpass 2,370 ten thousand tons of nineteen ninety-five.But with regard to present flue gas desulfurization technique, its investment and operating cost occupy high-leveled and difficult following, are difficult to promote, although cause environmental administration will strengthen SO year by year
2The fine dynamics of discharging, but can't fundamentally provide correlation technique to be solved.Present both at home and abroad industrialization and the flue gas desulfurization technique of studying have tens kinds approximately, and these methods can be divided into dry method and wet method on technology, can be divided into the method for abandoning and absorption method from the recycling that adds desulfurizing agent.Wherein the main method of industrialization or pilot scale has: 1) ammonium sulfite; 2) citrate method; 3) active carbon wet desulphurization; 4) phosphorus ammonia composite fertilizer is produced in wet desulphurization; 5) electronic beam method desulfurization; 6) lime-gypsum method desulfurization etc.Above method or investment are big, operating cost is high, be that waste desulfurizing agent can't utilize after the desulfurization, secondary pollution is arranged, for power plant's heavy duty boiler, the stacking of waste residue or be subjected to the restriction of freight charges or be subjected to the restriction that stack in the place, all be influence desulfur technology can business-like key factor.Therefore, these technology all are difficult to large-scale promotion and use in China at present.Wherein, the flue gas desulfurization technique lime-gypsum method of large-scale commercial applications application in the world, its technology maturity height, China also has power plant to introduce, but because cost height, big, not also none the example success of comprehensive utilization of by-product gypsum of investment.Most researchers thinks that the modified active semicoke is the most rising at present.
Relevant active carbocoal isoreactivity carbon based material removes SO in the flue gas
2Research, very active always both at home and abroad, domestic China Coal Research Institute Beijing coalification institute Li Wenhua, the Liu Chang of Inst. of Chemical Metallurgy, Chinese Academy of Sciences sees etc. and FDAC is made institute's five tastes constitution one, cell Wu Yong etc. and all done excessive quantity research work, some achievements have also been obtained, but they adopt traditional Activated Carbon Production method, and (water or oxygen activation under the high temperature) carries out modification to semicoke, causes the chemical property modification limited, simultaneously big (up to 40%), cost height of carbon loss.
Summary of the invention
At the shortcoming of above-mentioned absorbent charcoal based material preparation, the purpose of this invention is to provide a kind of efficient, inexpensive, absorbent charcoal based material SO that iterative regenerable recycles
2The preparation of adsorbent method.
A kind of medicament activation method prepares absorbent charcoal based material SO
2The method of adsorbent is characterized in that contenting carbon material is added the aqueous solution of chemical agent carrying out the high pressure hydrothermal chemistry modification in autoclave, and last drying activation makes.Described chemical agent is H
2O
2, H
2SO
4, HNO
3, HF, NaOH, KOH or KMnO
4Deng.
Described contenting carbon material is lignite semi-coke or anthracite, bituminous coal semicoke etc.; The bulk density of contenting carbon materials such as described lignite semi-coke or anthracite, bituminous coal semicoke is that 0.5-0.7g/ml, specific area are 10-200m
2/ g, carbon content are that 70-85%, hydrogen content are that 0.5-2.5%, oxygen content are that 10-30%, nitrogen content are that 0.3-1.2%, moisture are that 2-9%, content of ashes are that 3-15%, volatile matter content are 6-18%.
Its preparation process is as follows: the semicoke that will satisfy above-mentioned physicochemical condition obtains 4-10 purpose semicoke particle after screening, with semicoke particle and the chemical agent aqueous solution by volume 1: 0.6-1.2 mixes the back and adds autoclave, under 150-270 ℃, 6-43atm, react 1-8h, naturally take out the cooling back, makes 100-120 ℃ of down dry 2h activation then.
The activity of adsorbent and Sulfur capacity test are carried out in the fixed bed glass reactor, 20 millimeters of reactor inside diameter, and desulfurizing agent is the 4-8 order, and the desulfurizing agent admission space is 25ml, and the reactor beds layer height is 100mm, removes SO
2Temperature is 60-160 ℃, and air speed is 550-1500h
-1, grain/caliber is than being 0.1-0.13, flue gas consists of SO
21500-2200ppm, O
25%, H
2O 0-8%, all the other are by N
2Balance.Sulfur capacity is the accumulative total Sulfur capacity that equals calculating in 90% o'clock with desulfurization degree.
Characteristics of the present invention are carbon based material wide material sources such as semicoke, low price, and prepared adsorbent iterative regenerable recycles, and finally also can be used for wastewater treatment or boiler oil, non-secondary pollution.Can be widely used in the desulfurizing and purifying environmental protection industry of flue gases such as coal-burning power plant, coal-burning boiler and coal-fired furnace.As everyone knows, be " silicon materials " century last century, is likely the century of " raw material of wood-charcoal material " this century, and therefore, the present invention has a extensive future.
The specific embodiment
Describe the present invention in detail below by embodiment.
Embodiment 1:
The 4-10 order particle that semicoke is obtained after screening mixed back adding autoclave in 1: 0.83 by volume with the medicament mixed aqueous solution, and wherein the medicament mixed aqueous solution is respectively 3%, 5% and 6% aqueous hydrogen peroxide solution.270 ℃ of maximum temperatures, hydrothermal chemical reaction 2h under the maximum pressure 43atm, take out the cooling back naturally, measures its specific area and pore volume and desulphurizing activated then.The experiment condition of the activity of adsorbent and Sulfur capacity test: temperature: 85 ℃; Air speed: 900-1000h
-1SO
2Concentration: 1700-2100ppm; O
2:～5%; H
2O (g): 6-10%.The results are shown in Table 1.
The different H of table 1.
2O
2Absorbent charcoal based material SO under the concentration after the hydrothermal chemistry modification
2The variation of adsorbent specific area and pore volume and to the influence of time of break-through and Sulfur capacity
Sample raw material semicoke 3%H
2O
25%H
2O
26%H
2O
2
Specific area m
2/ g 49.19 335.9 431.3 234
Pore volume ml/g 0.0351 0.2297 0.2290 0.2399
Time of break-through h 1.5 7.2 8.5 7.0
Sulfur capacity gSO
2/ 100gC 0.68 5.6 6.4 5.11
As seen pass through the semicoke behind the medicament high pressure hydrothermal chemistry activation modification, Sulfur capacity can improve 8～10 times, and time of break-through has prolonged 5～6 hours.
Embodiment 2:
The 4-10 order particle that semicoke is obtained after screening mixed back adding autoclave in 1: 0.83 by volume with the medicament mixed aqueous solution, and wherein the medicament mixed aqueous solution is respectively 5% KOH, KMnO
4, HNO
3And H
2SO
4Solution.270 ℃ of maximum temperatures, hydrothermal chemical reaction 2h under the maximum pressure 43atm, take out the cooling back naturally, measures its specific area and pore volume and desulphurizing activated then.The experiment condition of the activity of adsorbent and Sulfur capacity test: temperature: 85 ℃; Air speed: 900-1000h
-1SO
2Concentration: 1700-2100ppm; O
2:～5%; H
2O (g): 6-10%.The results are shown in Table 2.
Absorbent charcoal based material SO under the different medicaments of table 2. after the hydrothermal chemistry modification
2The variation of adsorbent specific area and pore volume and to the influence of time of break-through and Sulfur capacity
Sample raw material semicoke KOH KMnO
4HNO
3H
2SO
4
Specific area m
2/ g 49.19 219 378 1,540 906
Pore volume ml/g 0.0351 0.2002 0.2042 0.4069 0.3062
Time of break-through h 1.5 5.0 6.2 4.5 4.5
Sulfur capacity gSO
2/ 100gC 0.68 4.21 2.51 2.78 2.56
Embodiment 3
Semicoke 4-10 order particle of obtaining after screening was mixed adding autoclave afterwards in 1: 0.83 by volume with 6% aqueous hydrogen peroxide solution, 270 ℃ of maximum temperatures, pressure be respectively 8,12,24,35 and 43atm under hydrothermal chemical reaction 2h, naturally take out the cooling back, measures its specific area and pore volume and desulphurizing activated then.The experiment condition of the activity of adsorbent and Sulfur capacity test: temperature: 85 ℃; Air speed: 900-1000h
-1SO
2Concentration: 1700-2100ppm; O
2:～5%; H
2O (g): 6-10%.The results are shown in Table 3.
Absorbent charcoal based material SO under table 3. different pressures after the hydrothermal chemistry modification
2The variation of adsorbent specific area and pore volume and to the influence of time of break-through and Sulfur capacity
Sample raw material semicoke 8atm 12atm 24atm 43atm
Specific area m
2/ g 49.19 468 689 906 234
Pore volume ml/g 0.0351 0.2364 0.2048 0.2160 0.2399
Time of break-through h 1.5 6.3 7.6 8.7 7.0
Sulfur capacity gSO
2/ 100gC 0.68 5.9 7.2 8.9 5.11
Claims (5)
1. a medicine activation method prepares absorbent charcoal based material SO
2The method of adsorbent is characterized in that contenting carbon material is added the aqueous solution of chemical agent carrying out the high pressure hydrothermal chemistry modification in autoclave, and last drying activation makes.
2. according to the described preparation of adsorbent method of claim 1, it is characterized in that wherein said contenting carbon material is lignite semi-coke or anthracite, bituminous coal semicoke etc.
3. according to the described preparation of adsorbent method of claim 1, it is characterized in that wherein said chemical agent is H
2O
2, H
2SO
4, HNO
3, HF, NaOH, KOH or KMnO
4Deng.
4. according to the described preparation of adsorbent method of claim 2, the bulk density that it is characterized in that wherein said lignite semi-coke or anthracite, bituminous coal semicoke is that 0.5-0.7g/ml, specific area are 10-200m
2/ g, carbon content are that 70-85%, hydrogen content are that 0.5-2.5%, oxygen content are that 10-30%, nitrogen content are that 0.3-1.2%, moisture are that 2-9%, content of ashes are that 3-15%, volatile matter content are 6-18%.
5. according to claim 1 or 2 described preparation of adsorbent methods, it is characterized in that described semicoke is obtained 4-10 purpose semicoke particle after screening, with semicoke particle and the chemical agent aqueous solution by volume 1: 0.6-1.2 mixes the back and adds autoclave, under 150-270 ℃, 6-43atm, react 1-8h, naturally take out the cooling back, makes 100-120 ℃ of down dry 2h activation then.
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|---|---|---|---|
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|---|---|
| CN1593744A true CN1593744A (en) | 2005-03-16 |
| CN100509141C CN100509141C (en) | 2009-07-08 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628202B (en) * | 2009-08-04 | 2011-09-28 | 北京大学 | Nanoparticle surface modified active semi-coke compound desulfurization denitrification agent and preparation method thereof |
| CN102580675A (en) * | 2012-02-21 | 2012-07-18 | 太原理工大学 | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon |
| CN102627277A (en) * | 2012-04-11 | 2012-08-08 | 太原理工大学 | Modified active carbon and method for removing ammonia gas in intensive livestock farm |
| CN102838115A (en) * | 2012-10-10 | 2012-12-26 | 江西财经大学 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
| CN103990434A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Active carbon propane adsorbent as well as preparation method and application thereof |
| CN106268741A (en) * | 2016-07-21 | 2017-01-04 | 常熟理工学院 | A kind of desulfurization catalyst of flue gas |
| CN107108232A (en) * | 2014-11-04 | 2017-08-29 | 新加坡国立大学 | Activated carbon, hydro-thermal charcoal and preparation method thereof |
| CN107970891A (en) * | 2017-12-01 | 2018-05-01 | 江苏省农业科学院 | One kind is based on malic acid and KMnO4The preparation method of the combined modified hot charcoal of cow dung biogas pulp water |
| CN109180989A (en) * | 2018-09-19 | 2019-01-11 | 肇庆凯艺装饰制品有限公司 | A kind of PS plastic foaming agent and preparation method thereof |
| CN110562978A (en) * | 2019-09-20 | 2019-12-13 | 安徽大学 | Method for modifying active carbon electrode material by composite aerobic acid hydrothermal method |
| CN114192114A (en) * | 2021-12-28 | 2022-03-18 | 山东亮剑环保新材料有限公司 | Preparation method of metal ion modified activated carbon desulfurizer |
| CN115672274A (en) * | 2022-11-09 | 2023-02-03 | 浙江工业大学 | Hydrothermal oxidation activated carbon, preparation method thereof and application thereof in cobalt-nickel extraction waste liquor |
-
2004
- 2004-06-24 CN CNB2004100244144A patent/CN100509141C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628202B (en) * | 2009-08-04 | 2011-09-28 | 北京大学 | Nanoparticle surface modified active semi-coke compound desulfurization denitrification agent and preparation method thereof |
| CN102580675B (en) * | 2012-02-21 | 2013-06-12 | 太原理工大学 | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon |
| CN102580675A (en) * | 2012-02-21 | 2012-07-18 | 太原理工大学 | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon |
| CN102627277A (en) * | 2012-04-11 | 2012-08-08 | 太原理工大学 | Modified active carbon and method for removing ammonia gas in intensive livestock farm |
| CN102838115B (en) * | 2012-10-10 | 2015-04-29 | 江西财经大学 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
| CN102838115A (en) * | 2012-10-10 | 2012-12-26 | 江西财经大学 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
| CN103990434A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Active carbon propane adsorbent as well as preparation method and application thereof |
| CN103990434B (en) * | 2014-05-16 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Active carbon propane adsorbent and its preparation method and application |
| CN107108232A (en) * | 2014-11-04 | 2017-08-29 | 新加坡国立大学 | Activated carbon, hydro-thermal charcoal and preparation method thereof |
| CN106268741A (en) * | 2016-07-21 | 2017-01-04 | 常熟理工学院 | A kind of desulfurization catalyst of flue gas |
| CN107970891A (en) * | 2017-12-01 | 2018-05-01 | 江苏省农业科学院 | One kind is based on malic acid and KMnO4The preparation method of the combined modified hot charcoal of cow dung biogas pulp water |
| CN109180989A (en) * | 2018-09-19 | 2019-01-11 | 肇庆凯艺装饰制品有限公司 | A kind of PS plastic foaming agent and preparation method thereof |
| CN110562978A (en) * | 2019-09-20 | 2019-12-13 | 安徽大学 | Method for modifying active carbon electrode material by composite aerobic acid hydrothermal method |
| CN114192114A (en) * | 2021-12-28 | 2022-03-18 | 山东亮剑环保新材料有限公司 | Preparation method of metal ion modified activated carbon desulfurizer |
| CN115672274A (en) * | 2022-11-09 | 2023-02-03 | 浙江工业大学 | Hydrothermal oxidation activated carbon, preparation method thereof and application thereof in cobalt-nickel extraction waste liquor |
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|---|---|
| CN100509141C (en) | 2009-07-08 |
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