CN1245243C - Highly effective defluorination agent for combustion coal smoke and preparation method thereof - Google Patents
Highly effective defluorination agent for combustion coal smoke and preparation method thereof Download PDFInfo
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- CN1245243C CN1245243C CN 03150302 CN03150302A CN1245243C CN 1245243 C CN1245243 C CN 1245243C CN 03150302 CN03150302 CN 03150302 CN 03150302 A CN03150302 A CN 03150302A CN 1245243 C CN1245243 C CN 1245243C
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Abstract
The present invention relates to a high efficiency fluoride-removing agent for coal-fired flue gas and a preparation method thereof. The proportion of raw materials is 60 to 80 wt% of calcium oxide, 60 to 80 wt% of calcium carbonate, 3 to 20 wt% of alumina, 3 to 10 wt% of silicon dioxide, 3 to 10 wt% of metallic oxide, 3 to 15 wt% of pore forming agent, 4 to 15 wt% of adhesive, 3 to 10 wt% of lubricating agent and water with the right amount, and fluorine compounds in flue gas can be removed by putting prepared honeycomb fluoride-removing agents in domestic coal boilers and flue channels of boilers. The fluoride-removing agent of the present invention can be prepared into geometric shapes with different sizes for being used by fuel channels with different sizes. The fluoride-removing agent of the present invention has porosity, and external appearance forms solids in a honeycomb structure. The present invention has the advantages of low cost and convenient use, the fluoride-removing efficiency is larger than 90%, and the service life is larger than three months.
Description
Technical field
The present invention relates to a kind of defluorinating agent and preparation method thereof, more particularly, relate to a kind of effectively cellular defluorinating agent and preparation method thereof of absorption of fluoride that household coal-stove or Industrial Boiler produce when coal-fired and oxysulfide pernicious gas that is used for.
Background technology
The fluoride gas severe contamination that gives off when burning high fluorine coal indoor-outdoor air, people live in the environment of high fluorine concentration for a long time, can influence health, easily cause the fluorine dental plaque, the fluorosis of bone disease.Fluoride (fluoride that especially industrial high fluorine coal combustion gives off) enters in the atmosphere, can increase the weight of the formation of acid rain, brings serious harm also for crops and City Building.
In the prior art adopt of Industrial Boiler fire coal added lime, Paris white, i.e. dry method defluorination more when burning.Dry method fluorine removing rate low (40-50%), easily slagging scorification, not easy to operate.The also available wet method defluorination of burning back flue gas.This method is flue gas to be made 10% slip liquid by lime or calcium carbonate.Make fluoride and calcium based compound solution reaction generate CaF
2Be deposited in the bottom, pond, this method fluorine removing rate can reach about 90%.But this method investment is many, and floor space is big, and labour intensity is big.
Technical scheme
The object of the present invention is to provide a kind of easy and simple to handle, inexpensive, dynamical cellular defluorinating agent and preparation method thereof, be used for flue gas defluorination (in the gas-phase reaction mode) behind briquet, coal dust, the hard coal to reduce the pollution of fluorine to atmosphere.
The objective of the invention is to reach by the following technical programs:
A kind of coal-fired flue-gas high performance agent for removing fluorin, its proportion of raw materials is:
(1). calcium oxide and calcium carbonate: 60～80Wt%
(2). aluminium oxide: 3～20Wt%
(3). silica: 3～10Wt%
(4). metal oxide: 3～10Wt%
(5). pore creating material: 3～15Wt%
(6). adhesive: 4～15Wt%
(7). lubricant: 3～10Wt%
(8). water is an amount of.
A kind of preferred coal-fired flue-gas high performance agent for removing fluorin, its proportion of raw materials is:
(1). calcium oxide and calcium carbonate: 66～68Wt%
(2). aluminium oxide: 5～18Wt%
(3). silica: 5～8Wt%
(4). metal oxide: 5～8Wt%
(5). pore creating material: 5～12Wt%
(6). adhesive: 5～12Wt%
(7). lubricant: 4～8Wt%
(8). water is an amount of.
A kind of preferred especially coal-fired flue-gas high performance agent for removing fluorin, its proportion of raw materials is:
(1). calcium oxide and calcium carbonate: 67Wt%
(2). aluminium oxide: 8Wt%
(3). silica: 5Wt%
(4). metal oxide: 5Wt%
(5). pore creating material: 5Wt%
(6). adhesive: 5Wt%
(7). lubricant: 5Wt%
(8). water is an amount of.
Described pore creating material can be: starch, carboxymethyl cellulose; Described adhesive can be: starch, carboxymethyl cellulose or waterglass; Described lubricant can be: machine oil, tung oil or ethylene glycol; Described metal oxide can be magnesia or manganese dioxide.
The weight ratio of described calcium oxide and calcium carbonate is 1:3～3: 1, preferred 2.5: 1.
A kind of preparation method of coal-fired flue-gas high performance agent for removing fluorin, its step is as follows:
(1) with the calcium oxide of 60～80Wt%: the weight of calcium carbonate ratio is that 1: 3～3: 1 mixture, the aluminium oxide of 3～20Wt%, the silica of 3～10Wt% and the metal oxide of 3～10Wt% are pulverized sieve (100 order), stirring and evenly mixing;
(2) mix the pore creating material of 3～15Wt%, the adhesive of 4～15Wt%, lubricant and the suitable quantity of water of 3～10Wt%, in vacuum pugmill, stir into the plasticity pug;
(3) leave standstill slaking;
(4) through becoming punch die compression moulding;
(5) sintering activation.
Coal-fired flue-gas high performance agent for removing fluorin of the present invention is with calcium oxide (CaO), calcium carbonate (CaCO
3) be primary raw material, with aluminium oxide (neutral or alkaline Al
2O
3) and silica (SiO
2) be skeleton, add metal oxide (MgO, MnO
2), be mixed with pore creating material, adhesive, lubricant and water, mixing is made the plasticity pug, be convenient to compression moulding, be pressed into the different geometry such as cylindrical, square, fan-like pattern and the defluorinating agent of seriation size, make cavernous solid defluorinating agent after the activated again processing through mould.This kind defluorinating agent permeability is good, and resistance is little, and bigger adsorption surface area and stronger compressive resistance are arranged.
The chemical reaction of HF in defluorinating agent is:
Also discharge during coal combustion than the oxysulfide of fluoridizing hundreds of times of object heights, the chemical reaction by coal-fired flue-gas high performance agent for removing fluorin of the present invention the time is:
Coal-fired flue-gas high performance agent for removing fluorin of the present invention can be removed fluoride and the oxysulfide more than 90%, till the calcium in defluorinating agent runs out of.
The effect that patent of the present invention compared with prior art can reach:
(1) defluorinating agent is that gas one solidifies reaction, and fluorine removing rate reaches more than 90%;
(2) composition and structure advanced person are used for the flue gas defluorination, do not need special attachment device;
(3) there is not the drawback of secondary row fluorine, because defluorinating agent is to use and generate calcirm-fluoride (＞1300 ℃ begin to decompose) and calcium sulfate (＞900 ℃ begin decomposition), section H F and SO at last in flue
2Still be present in the flue gas and discharge through flue.
(4) the defluorinating agent waste residue is recycling.
The invention will be further described below by drawings and Examples, but do not mean that limitation of the present invention.
Description of drawings
Fig. 1 represents cylinder bodily form defluorinating agent;
Fig. 2 represents the segment defluorinating agent;
Fig. 3 represents the square defluorinating agent;
Fig. 4 represents according to Industrial Boiler smoke evacuation chimney internal diameter size, selects cylinder and segment with the bonding defluorinating agent that forms of waterglass;
Fig. 5 represents with four bonding defluorinating agents that form of square defluorinating agent;
Fig. 6 represents that defluorinating agent is used in the embodiment in the commercial coal stove flue;
Fig. 7 represents that defluorinating agent is used in the embodiment in the Industrial Boiler flue;
Fig. 8 represents the curve map in service life of defluorinating agent of the present invention.
The specific embodiment
As shown in Figure 1, calcium oxide and calcium carbonate (its ratio is 1: 3), the aluminium oxide of 8Wt%, the silica of 5Wt% and the magnesia of 5Wt% of 66Wt% are pulverized sieve (100 order), stirring and evenly mixing; Mix the carboxymethyl cellulose pore creating material of 5Wt%, the amylum adhesive of 6Wt%, oil lubricating agent and the suitable quantity of water of 5Wt%, in vacuum pugmill, stir into the plasticity pug; Leave standstill slaking; Through becoming punch die compression moulding; The sintering activation; Become cylinder bodily form defluorinating agent shown in Figure 1.Its diameter 80-160 millimeter, (or length) 50-350 millimeter highly, the aperture is the 8-20 millimeter, hole and pitch of holes (hole wall) they are the 5-20 millimeter.
As shown in Figure 2, calcium oxide and calcium carbonate (its ratio is 3: 1), the aluminium oxide of 10Wt%, the silica of 7Wt% and the manganese dioxide of 8Wt% of 60Wt% are pulverized sieve (100 order), stirring and evenly mixing; Mix the starch pore creating material of 6Wt%, the carboxymethyl cellulose binder of 6Wt%, tung oil lubricant and the suitable quantity of water of 3Wt%, in vacuum pugmill, stir into the plasticity pug; Leave standstill slaking; Through becoming punch die compression moulding; The sintering activation; Become segment defluorinating agent shown in Figure 2.Its dimension series a=63-160 millimeter, the b=125-360 millimeter, the c=40-160 millimeter, the d=200-350 millimeter, the aperture is the 8-20 millimeter, hole and pitch of holes (hole wall) they are the 5-20 millimeter.
As shown in Figure 3, calcium oxide and calcium carbonate (its ratio is 2.5: 1), the aluminium oxide of 4Wt%, the silica of 4Wt% and the magnesia of 3Wt% of 77Wt% are pulverized sieve (100 order), stirring and evenly mixing; Mix the carboxymethyl cellulose pore creating material of 5Wt%, the water glass binder of 4Wt%, glycol lubricant and the suitable quantity of water of 3Wt%, in vacuum pugmill, stir into the plasticity pug; Leave standstill slaking; Through becoming punch die compression moulding; The sintering activation; Become square defluorinating agent shown in Figure 3.Its dimension series a=100-250 millimeter, the b=100-250 millimeter, the c=100-250 millimeter, the aperture is the 8-20 millimeter, hole and pitch of holes (hole wall) they are the 5-20 millimeter.
An embodiment 1 gained cylinder bodily form defluorinating agent and 3 embodiment 2 gained segment defluorinating agents are formed with waterglass is bonding, as shown in Figure 4.
With bonding the forming of 4 embodiment, 3 gained square defluorinating agents, as shown in Figure 5.
Embodiment 6
As shown in Figure 6, embodiment 1 gained cylinder bodily form defluorinating agent is used in the commercial coal stove flue; Wherein 1 is stove and accessory, and 2 is defluorinating agent, and 3 is flue, and 4 is ring flange.
Embodiment 7
As shown in Figure 7, embodiment 1 gained cylinder bodily form defluorinating agent is used in the Industrial Boiler flue, wherein 1 is boiler, and 2 is blower fan, and 3 is flue, and 4 is defluorinating agent, and 5 is ring flange.
The physical property of defluorinating agent of the present invention:
(1). defluorinating agent shape: cylinder, square, segment
(2). hole shape: circular hole
(3). front openings rate: 45-48%
(4). specific area: 9.0-9.3m
2/ g
(5). pore volume: 0.024-0.028ml/g
(6). average micropore size: 106-110A
(7). water absorption rate: 40-42%
(8). malleation intensity: 14.9-16.4kg/cm
2
The using method of defluorinating agent of the present invention:
Can be when using defluorinating agent of the present invention according to the size and dimension of flue caliber, select one identical with the flue internal diameter, the bottom is netted, there is the pipeline (in pack into defluorinating agent) of ring flange at two ends, and with flue and stove and accessory outlet with screw fixed flange up and down, both can finish the preparation of defluorination work, after defluorinating agent is entirely ineffective, the defluorinating agent that more renews again.The 300 gram defluorinating agents (86 millimeters of diameters, 100 millimeters in length) of packing in the each household flue burn 6-8 kilogram honeycomb briquette every day.Fluorine removing rate can use more than 3 months continuously more than 90%; This defluorinating agent is all right sulphur removal in defluorination, and sulfur removal effectiveness is more than 90%, (the sulphur removal life-span is about 1 month).
The life-span that industry coal-boiler uses defluorinating agent and fluorine removing rate (more than 90%) with day a Coal-fired capacity, coal fluorinated volume, coal sulfur content, flue gas flow rate relevant, thereby select the defluorinating agent of different apertures, different length for use.
When selective oxidation calcium or Paris white (industrial), should select calcium content height, calcium oxide or Paris white that fluorinated volume is low, make by above-mentioned defluorinating agent process ratio, to guarantee higher fluorine removing rate and service life.
The application example of defluorinating agent of the present invention:
1. pack in the coal stove flue defluorination and the sulfur removal effectiveness of different length defluorinating agent.
At rural area burning honeycomb briquette (coal: native=3: 1) and hard coal, detect defluorination, the sulfur removal effectiveness of different length defluorinating agent.Measure content of fluoride in the air with Fluoride ion selective electrode method; With tetrachloro mercury sodium---hydrochloric acid Pararosaniline colorimetric method (GB8970-88) is measured content of sulfur dioxide in the air.The results are shown in Table 1.
The defluorination and the sulfur removal effectiveness of table 1 different length defluorinating agent
| Coal | Defluorinating agent | Before the defluorination | Behind the defluorination | Fluorine removing rate (%) | Before the sulphur removal | After the sulphur removal | Sulfur removal effectiveness (%) | |||||
| Long (cm) | The piece number | Sample number | Fluorine concentration (mg/m 3) | Sample number | Fluorine concentration (mg/m 3) | Sample number | SO2 concentration (mg/m 3) | Sample number | SO2 concentration (mg/m 3) | |||
| | 4 4 8 | 1 2 1 | 3 17 6 | 12.77 11.23 12.48 | 3 17 6 | 0.81 0.27 0.27 | 93.7 97.7 97.8 | 13 | 42.08 | 15 | 4.84 | 89.0 |
| Hard coal | 8 | 1 | 3 | 11.73 | 3 | 0.23 | 98.0 | |||||
As seen from Table 1, the fluorine removing rate of the cellular defluorinating agent of this kind is all very high.Increase defluorinating agent length, fluorine removing rate increases thereupon.
2. service life of defluorinating agent of the present invention (time)
In the man of peasant household of endemia fluorosis district occurred frequently, rural area, burn the 8Kg honeycomb briquette every day, respectively gather 3 fluorides and sulfur dioxide air sample at the forward and backward flue thief hatch of defluorinating agent, measure content of fluoride in the air with Fluoride ion selective electrode method; With tetrachloro mercury sodium---hydrochloric acid Pararosaniline colorimetric method (GB8970-88) is measured content of sulfur dioxide in the air.Calculate average fluorine removing rate and sulfur removal effectiveness, and draw the curve in service life of defluorinating agent, as shown in Figure 8.
As can be seen from Figure 8, the fluorine removing rate of defluorinating agent of the present invention＞90%, defluorination life-span＞3 month; Sulphur removal life-span＞90% of defluorinating agent of the present invention, the sulphur removal life-span is one month.
Claims (5)
1, a kind of coal-fired flue-gas high performance agent for removing fluorin, it is characterized in that: its proportion of raw materials is:
(1). calcium oxide and calcium carbonate: 60～80Wt%
(2). aluminium oxide: 3～20Wt%
(3). silica: 3～10Wt%
(4). magnesia or manganese dioxide: 3～10Wt%
(5). starch or carboxymethyl cellulose: 3～15Wt%
(6). starch, carboxymethyl cellulose or waterglass: 4～15Wt%
(7). machine oil, tung oil or ethylene glycol: 3～10Wt%
(8). surplus is a water.
2, according to the described coal-fired flue-gas high performance agent for removing fluorin of claim 1, the content that it is characterized in that calcium oxide described in the described raw material and calcium carbonate is 67Wt%; The content of described aluminium oxide is 8Wt%; The content of described silica is 5Wt%; The content of described magnesia or manganese dioxide is 5Wt%; The content of described starch or carboxymethyl cellulose is 5Wt%; The content of described starch, carboxymethyl cellulose or waterglass is 5Wt%; Described machine oil, tung oil or glycol content are 5Wt%.
3, according to each described coal-fired flue-gas high performance agent for removing fluorin among the claim 1-2, the weight ratio that it is characterized in that described calcium oxide and calcium carbonate is 1: 3～3: 1.
4, according to the described coal-fired flue-gas high performance agent for removing fluorin of claim 3, the weight ratio that it is characterized in that described calcium oxide and calcium carbonate is 2.5: 1.
5, a kind of preparation method of coal-fired flue-gas high performance agent for removing fluorin, its step is as follows:
(1) with the calcium oxide of 60～80Wt%: the weight of calcium carbonate ratio is that 1: 3～3: 1 mixture, the aluminium oxide of 3～20Wt%, the silica of 3～10Wt% and magnesia or the manganese dioxide of 3～10Wt% are pulverized, and sieves stirring and evenly mixing;
(2) mix the starch of 3～15Wt% or carboxymethyl cellulose, starch, carboxymethyl cellulose or the waterglass of 4～15Wt%, machine oil, tung oil or ethylene glycol and the suitable quantity of water of 3～10Wt%, stir into the plasticity pug;
(3) leave standstill slaking;
(4) through becoming punch die compression moulding;
(5) sintering activation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150302 CN1245243C (en) | 2003-07-24 | 2003-07-24 | Highly effective defluorination agent for combustion coal smoke and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150302 CN1245243C (en) | 2003-07-24 | 2003-07-24 | Highly effective defluorination agent for combustion coal smoke and preparation method thereof |
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|---|---|
| CN1569311A CN1569311A (en) | 2005-01-26 |
| CN1245243C true CN1245243C (en) | 2006-03-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101810991B (en) * | 2010-04-14 | 2011-10-05 | 太原理工大学 | Method for preparing chlorine trapping and eliminating powder |
| CN105597656B (en) * | 2016-02-14 | 2018-06-08 | 常州清流环保科技有限公司 | A kind of method for preparing defluorinating agent using polyaluminium chloride production residue |
| CN106382648A (en) * | 2016-12-05 | 2017-02-08 | 温州乐享科技信息有限公司 | Coal combustion method |
| CN109201703A (en) * | 2018-09-17 | 2019-01-15 | 新疆生产建设兵团第八师天山铝业股份有限公司 | A kind of curing agent of electrolytic aluminium slag from delining soluble fluorine |
| CN109758902A (en) * | 2019-03-16 | 2019-05-17 | 武汉禾谷环保有限公司 | A kind of defluorinating agent and preparation method thereof |
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