CN100404653C - Method for removing mercury from fired coal by biological method - Google Patents
Method for removing mercury from fired coal by biological method Download PDFInfo
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- CN100404653C CN100404653C CNB2006100245127A CN200610024512A CN100404653C CN 100404653 C CN100404653 C CN 100404653C CN B2006100245127 A CNB2006100245127 A CN B2006100245127A CN 200610024512 A CN200610024512 A CN 200610024512A CN 100404653 C CN100404653 C CN 100404653C
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Abstract
The present invention relates to a method for removing mercury from fired coal by a biological method. The present invention removes mercury from fired coal by dissolving mercury in pulverized fired coal in the way of utilizing sulfuric acid generated under the condition of preprocesing mixed thiobacilli strains without adding acid. Firstly, 0.2 to 1% of element sulfur is put into waste water or sludge according to a volume ratio, and thiobacilli is made to proliferate for generating sulfuric acid under the aerobic condition of a reactor; discharged mixed liquid is filled into a coal processor, and then mercury in pulverized coal is removed under the conditions of aeration and above 1.5 mg/L of dissolved oxygen. The method of the present invention is carried out at normal temperature without carrying out acidification preprocessing, and has the advantages of continuous running, simple and convenient operation, good operating environment and low cost. Most mercury in coal can be removed by processing for 2 to 3 days.
Description
Technical field
The present invention relates to a kind of biological process and remove the method for mercury in the fire coal, be specifically related to a kind ofly utilize the mix sulphur bacillus that fire coal is removed the method for mercury, belong to field of environment engineering technology.
Background technology
All have a certain amount of mercury in the coal, according to domestic and international pertinent data, the content of mercury is according to the difference in its place of production in the coal, and mercury content is 0.01mg-3.3mg in the per kilogram coal.Under the hot conditions, mercury has very strong volatility, and in coal combustion process, wherein the mercury of 30-75% can enter in the atmosphere with gaseous form.Because a large amount of uses of coal, the whole world surpasses 600 tons because of coal to atmospheric year discharging mercury amount, and as seen, the mercury that discharges in the coal has become the important source of mercury in the atmosphere, and atmospheric environment is caused severe contamination.
At present, the removal of mercury mainly contains removal methods such as hot pre-treatment and sour pre-treatment in the coal, the shortcoming of these methods is running cost height, envrionment conditions is unfriendly, be easy to produce secondary pollutant (AkiraIwashita in the treating processes, Shomei Tanamachi, Tsunenori Nakajima, Hirokazu Takanashi, Akira Ohki, Removal of mercury from coal by mild pyrolysis and leaching behavior of mercury, Fuel 83 (2004) 631-638.).Biological harmless is handled the research of coal, though idol has report, but still fail to break away from the way of acidification in advance, and from existing a small amount of report, microorganism used therefor also only is that certain bacterial strain is providing the research (Dronen of result of use under the defined medium, L.C.et al.Anassessment of acid wash and bioleaching pretreating options to remove mercury fromcoal, Fuel, 2004,83, (2), 18i 186.).
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of biological process to remove the method for mercury in the fire coal, adopt lower running cost, reach higher mercury removal efficient, easy to operate, the operating environment friendliness.
Be to realize this purpose, the present invention utilizes the mix sulphur bacillus strain not adding the sulfuric acid that produces under the sour pretreated condition, will be through the mercury stripping in the fire coal of pulverization process, thus realize the removal of mercury in the fire coal.At first in sewage or mud, volume ratio adds 0.2%~1% elementary sulfur by weight, and under the aerobic conditions of reactor, make thiobacillus obtain propagation and generation sulfuric acid, the mixed solution of deriving is introduced in the coal treater, at aeration and dissolved oxygen is higher than under the condition of 1.5mg/L, the coal through pulverization process is carried out demercuration handle.Through 2-3 days processing, coal can reach the higher effect that removes mercury.
Technical scheme of the present invention comprises the following step:
1, gets municipal sewage plant's sewage or municipal sewage plant mud without dehydration, with 0.2%~1.0% (weightmeasurement ratio of sulphur and sewage or mud, w/v) amount addition element sulphur, carrying out the aeration domestication in bio-reactor cultivates, when the pH of sewage or mud value is lower than 2.0, promptly obtain required domestication thiobacillus mixed-culture medium.
2, (weightmeasurement ratio of sulphur and sewage or mud, the sewage or the mud of amount addition element sulphur w/v) import bio-reactor by the Continuous Flow mode and carry out continuous relieving haperacidity, carry out continuous aeration by aerating apparatus simultaneously will to press 0.2%~1%.
3, the mixed solution in the reactor is derived, and introduce in the coal treater, at aeration and dissolved oxygen is higher than under the condition of 1.5mg/L, the coal through pulverization process is removed the processing of mercury, the treatment time was generally 2~3 days.
4, uses of can burning of the coal after demercuration is handled, the supernatant liquor after stripping is handled can carry out physics and chemistry method (chemical precipitation, the electrolysis) aftertreatment of routine, carries out the recovery of mercury.
For further reducing big production cost, improve treatment effect, can carry out the thiobacillus amplification cultivation to the domestication thiobacillus mixed-culture medium of above-mentioned the first step gained handles, method is the nutrient solution of will tame processing by 1%~5% the amount (volume ratio of sulphur and sewage or mud, v/v) render in the sewage or liquid sludge that continuously flows in the big volume bio-reactor, add elementary sulfur by 0.2%~1.0% amount (the weightmeasurement ratio w/v of sulphur and sewage or mud) simultaneously, carried out air culture and supported, the pH value of sewage or mud is lower than 2.0 in big volume bio-reactor.And then continued for second step, in big volume bio-reactor, advance sewage or the mud that has added 0.2%~1.0% (w/v) elementary sulfur continuously, carry out continuous relieving haperacidity.
Coal carries out demercuration in the coal treater, the use of can burning of the coal after the processing.The a small amount of suspended solids that exists in sewage or the mud enters the coal treater, can be with the coal use of burning.
Main points of the present invention are, with the nutritive salt itself that contain in sewage or the mud and the elementary sulfur of interpolation is growth of thiobacillus matrix, thiobacillus is bred in a large number, elementary sulfur is converted into sulfuric acid by thiobacillus, sulfuric acid that utilization produces in this process and thiobacillus are handled coal, sulfuric acid can produce the leaching effect to the simple substance mercury that exists in the coal, thiobacillus then under aerobic conditions (dissolved oxygen is higher than 1.5mg/L) by the utilization of sulphur in to sulfide, make the mercury that exists with sulfide obtain to separate, effect by sulfuric acid and thiobacillus, mercury in the coal can obtain to remove, thereby realizes the removal of mercury in the coal.
Positively effect of the present invention is: sewage or mud are the environmental pollutant that need infusion of financial resources to handle originally, but the thiobacillus that wherein contains original inhabitants, the present invention utilizes the physilogical characteristics of this point and combined sulfur bacillus just, breed and relieving haperacidity, the mercury in the coal is removed processing with the acid of gained.The present invention compares with other method, and operation need not add sour pre-treatment at normal temperatures, continuously-running, and running cost is low, and is easy and simple to handle, the operating environment friendliness.Processing through 2~3 days, can make the mercury in the coal obtain to remove largely, the mercury removal rate can reach more than 32%~73% and (becomes according to the difference of coal mercury content) after handling 2 days, handle after 3 days, can reach more than 38%~82% and (become) according to the difference of coal mercury content.
Description of drawings
Accompanying drawing 1 is a process flow sheet of the present invention.
Among Fig. 1,1 is bio-reactor, and 2 is the coal treater, and 3 for producing sour pond aerating apparatus, and 4 is sewage or mud inlet tube, and 5 is the mixed solution delivery line, and 6 is mercurous supernatant liquor delivery line, and 7 is demercuration coal take-off equipment, and 8 is coal treating pond aerating apparatus.
Embodiment
Technical process of the present invention as shown in Figure 1.As seen from Figure 1, the device that technical process of the present invention is adopted mainly comprises bio-reactor 1, coal treater 2 etc., bio-reactor 1 is introduced sewage or the mud that is mixed with 0.2%~1.0% (w/v) elementary sulfur by inlet tube 4, link to each other with coal treater 2 by mixed solution delivery line 5, coal treater 2 is sent the recycling that supernatant liquor carries out mercury by supernatant liquor delivery line 6, demercuration coal take-off equipment 7 output demercuration coals by the top, aerating apparatus 8 is installed on the coal treater 2, and bio-reactor 1 also is connected with the sour pond of product aerating apparatus 3.
Technology operating procedure of the present invention is: the sewage or the mud that add 0.2%~1% (w/v) elementary sulfur are housed in the bio-reactor 1, and acidifying has been that pH is lower than 2.0, to be mixed with the sewage or the mud of 0.2%~1% (w/v) elementary sulfur equally, import in the reactor 1 by the Continuous Flow mode, and carry out continuous aeration by aerating apparatus 3, simultaneously the mixed solution in the reactor 1 is derived by mixed solution delivery line 5, and introduce in the coal treater 2, will be in the coal treater soak into through the coal of pulverizing, under the aeration condition that starts aerating apparatus 8 (dissolved oxygen is higher than 1.5mg/L) carry out the processing that removes of mercury in the coal.Coal is after demercuration is handled, and demercuration coal is by take-off equipment 7 outputs, and supernatant liquor is derived the mercury recycling of carrying out ordinary method by delivery line 6.
Below by specific embodiment technical scheme of the present invention is described further.
Get Shanghai Sewage Plant sewage, the elementary sulfur that adds 1.0% (w/v), carrying out aeration in bio-reactor 1 cultivated after 22 days, advance sewage (ratio in 1% (w/v) adds elementary sulfur) continuously, effusive mixed solution is after centrifugal treating, and its parting liquid is used for mercurous bottle coal for the lean coal of 0.738mg/Kg, mercurous 0.152mg/Kg and carries out the demercuration processing.Coal after handling in 2 days, and mercury in lean coal and the bottle coal is reached respectively 64%, 32% removal.After handling in 3 days, mercury in lean coal and the bottle coal is reached respectively 76%, 38% removal.
Get Shanghai Sewage Plant solid content and be 2.7% liquid sludge, the elementary sulfur (w/v) of adding 0.2%, carrying out aeration in bio-reactor cultivated after 22 days, advance mud (ratio in 0.2% (w/v) adds elementary sulfur) continuously, the mud extraction parting liquid is used for mercurous bottle coal for the lean coal of 0.738mg/Kg, mercurous 0.152mg/Kg and carries out the demercuration processing.Coal after handling in 2 days, and mercury in lean coal and the bottle coal is reached respectively 68%, 36% removal.After handling in 3 days, mercury in lean coal and the bottle coal is reached respectively 73%, 41% removal.
Get Shanghai Sewage Plant solid content and be 2.7% liquid sludge, the elementary sulfur (w/v) of adding 1.0%, carrying out aeration in bio-reactor cultivated after 22 days, advance mud (ratio in 1% (w/v) adds elementary sulfur) continuously, the mud extraction parting liquid is used for mercurous bottle coal for the lean coal of 0.738mg/Kg, mercurous 0.152mg/Kg and carries out the demercuration processing.Coal after handling in 2 days, and mercury in lean coal and the bottle coal is reached respectively 73%, 39% removal.After handling in 3 days, mercury in lean coal and the bottle coal is reached respectively 82%, 43% removal.
Claims (2)
1. a biological process is removed the method for mercury in the fire coal, it is characterized in that comprising the following step:
1) gets sewage work's sewage or sewage work mud without dehydration, with the weightmeasurement ratio w/v of sulphur and sewage or mud 0.2%~1% amount addition element sulphur, in bio-reactor, carry out aeration and be cultured to the pH value and be lower than 2.0, obtain taming the thiobacillus mixed-culture medium;
2) will be the sewage or the mud of 0.2%~1% amount addition element sulphur by the weightmeasurement ratio w/v of sulphur and sewage or mud, import reactor by the Continuous Flow mode and carry out continuous relieving haperacidity, and carry out continuous aeration by aerating apparatus;
3) mixed solution in the reactor is derived, and introduce in the coal treater, at aeration and dissolved oxygen is higher than under the condition of 1.5mg/L the coal through pulverization process is carried out demercuration and handles, the treatment time is 2~3 days;
4) coal after demercuration is handled is used for burning, and the supernatant liquor after stripping is handled carries out the recycling of mercury with conventional physics and chemistry method.
2. remove the method for mercury in the fire coal according to the biological process of claim 1, it is characterized in that the domestication thiobacillus mixed-culture medium of gained is carried out the amplification cultivation processing, 's 1%~5% amount with the nutrient solution of taming processing by the volume ratio v/v of sulphur and sewage or mud, render in the sewage or mud that continuously flows in the big volume bio-reactor, be that 0.2%~1% amount adds elementary sulfur by the weightmeasurement ratio w/v of sulphur and sewage or mud simultaneously, having carried out air culture supports, the pH value of sewage or mud is lower than 2.0 in big volume bio-reactor, carries out continuous relieving haperacidity again.
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CN1270077A (en) * | 1999-03-31 | 2000-10-18 | 麦克德莫技术股份有限公司 | Method for eliminating mercury from flue gas by using sulphureous gas and liquid |
CN1698931A (en) * | 2005-04-07 | 2005-11-23 | 上海交通大学 | Flue gas hydrargyrum-removing method by catalytic oxidation |
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CN1270077A (en) * | 1999-03-31 | 2000-10-18 | 麦克德莫技术股份有限公司 | Method for eliminating mercury from flue gas by using sulphureous gas and liquid |
CN1698931A (en) * | 2005-04-07 | 2005-11-23 | 上海交通大学 | Flue gas hydrargyrum-removing method by catalytic oxidation |
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