CN101003757B - Electrochemical regulating and controlling method and equipment of biological desulphurization for coal - Google Patents
Electrochemical regulating and controlling method and equipment of biological desulphurization for coal Download PDFInfo
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- CN101003757B CN101003757B CN2006101664861A CN200610166486A CN101003757B CN 101003757 B CN101003757 B CN 101003757B CN 2006101664861 A CN2006101664861 A CN 2006101664861A CN 200610166486 A CN200610166486 A CN 200610166486A CN 101003757 B CN101003757 B CN 101003757B
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Abstract
This invention discloses method and apparatus for electrochemically controlled biological desulfurization of coal. The method comprises: catalytically domesticating desulfurization bacteria solution in a catalytic domesticator applied with electric field, amplification-culturing in an amplification-culture device, and performing biological treatment on coal by using the desulfurization bacteria solution in a reverse-flow extraction device. Electrochemical domestication and amplification culture can accelerate the metabolic rate of the desulfurization bacteria solution, thus can shorten the desulfurization time and increase the desulfurization efficiency. The apparatus comprises: a front electrochemical catalytic domesticator and a controller, a middle amplification culture device and a controller, a back reverse-flow extraction device, a circulation feedback heater, an air-feeding controller, a pH regulator, a sulfur recovery device, and an air sterilizer. This invention introduces microbe technique and electrochemical method into coal desulfurization process, thus can regulate bacteria activity as well as coal and pyrite surface properties. This invention has such advantages as easy operation, simple apparatus, accurate control, timely feedback, high bacteria propagation rate, and high desulfurization efficiency.
Description
Technical field
The present invention relates to a kind of sulfur method and the specific equipment of coal, the sulfur dioxide pollution problem that causes at current fire coal and a kind of electrochemical regulating and controlling biological desulphurization for coal method and the device developed.
Background technology
At present, the desulfurization before combustion method of coal mainly contains physics doctor treatment, chemical desulfurization method and biological desulphurization method.
The physics doctor treatment mainly is to carry out coal desulfurization by the difference of coal and pyrite density, magnetic, electroconductibility and interfacial property, this method can only remove most of inorganic sulfur wherein under present technical qualification, and can't remove its organosulfur, and energy consumption is higher, device systems is huge, and the factor that restricts, influences desulfurization is many.
The chemical desulfurization method is to be aided with high temperature or high pressure by chemical process, decomposes and removes organosulfur and inorganic sulfur in the coal through chemical action, though this method efficient is higher, complex process, cost height, secondary pollution are serious.
The biological desulphurization for coal method is that a kind of environmental friendliness, energy consumption are low, the method that secondary pollution is few, application potential is big.In the biological desulphurization of coal, mainly be to utilize some aerobic, as to have a liking for acid chemosynthetic autotroph Thiobacillus biology, as thiobacillus ferrooxidant, abbreviate T.f bacterium or thiobacillus thiooxidant as, carry out desulfurization with direct, indirect or combined action mechanism, reach the desulfurization purpose by the water-soluble cpds that generates sulfur-bearing.Yet because thiobacillus ferrooxidant is a chemoautotrophic bacteria, its growth and breeding speed is slow, Oxidation of Fe
2+Speed is low, thereby its industrial application is restricted.
Summary of the invention
The objective of the invention is to solve the desulfurizing and purifying problem of coal,, provide the electrochemical regulating and controlling biological desulphurization for coal method and the device of a kind of efficient, less energy-consumption, non-secondary pollution for removing inorganic sulfur and the organosulfur in the coal in processing, in transforming, utilizing.
The equipment scheme that solves its technical problem is: agent set comprises leading portion electrochemical catalysis domestication device, stage casing amplification good child-rearing device, back segment adverse current leaching device; Auxiliary facility comprises that the good child-rearing control device is amplified in leading portion electrochemistry domestication control device, stage casing, heating unit, gas transmission control device, pH control device, sulfur recovery unit and air bacterial filter devices are fed back in three sections temperature control units, circulations; Leading portion electrochemical catalysis domestication device is connected with three sections temperature control units with leading portion electrochemistry domestication control device simultaneously, the stage casing is amplified the good child-rearing device and is amplified the good child-rearing control device with the stage casing simultaneously, three sections temperature control units, the gas transmission control device is connected with the pH control device, back segment adverse current leaching device is connected with sulfur recovery unit with three sections temperature control units, three sections temperature control units are by circulation feedback heating unit and leading portion electrochemical catalysis domestication device, the stage casing is amplified the good child-rearing device and is connected with back segment adverse current leaching device, leading portion electrochemical catalysis domestication device, the overcoat that good child-rearing device and back segment adverse current leaching device are amplified in the stage casing passes through pipeline, valve is connected, and the gas transmission control device amplifies good child-rearing device with leading portion electrochemical catalysis domestication device with the stage casing by air bacterial filter device and is connected.
Described leading portion electrochemical catalysis domestication device comprises electrochemistry control device and catalysis domestication device, in the electrochemistry control device (1), catalysis electrode links to each other with data-carrier store and controller with potentiometric controller, and by serial communication interface with data transmission to computer, utilize it to gather feedback system and analysis software control electrochemical parameter; In the catalysis domestication device (6) catalysis three electrodes, thermopair and pneumatic mixed plate are housed, outside catalysis domestication device, three charging and discharging control valves are arranged, a water cycle heating jacket; Catalysis three electrodes of catalysis domestication device are connected with the electrochemistry control device, and thermopair is connected with three sections temperature control units, in the bottom of catalysis domestication device (6) pneumatic mixing tank is installed.
Described stage casing is amplified the good child-rearing control device and is comprised stage casing domestication control device (2) and stage casing amplification good child-rearing control device (7), in the stage casing domestication control device (2), two apparent constant voltage/current isolators connect reference electrode and working electrode, amplify good child-rearing device (7) to the stage casing and add volta potential; Amplify in the stage casing four charging and discharging control valves, pneumatic mixing tank, water cycle heating jacket outside the good child-rearing device (7); Amplify in the good child-rearing device (7) in stage casing amplification control device (2) and stage casing has the sheet two electrodes to be connected, soda acid supply shower nozzle is installed in the top that good child-rearing device (7) is amplified in the stage casing, the feedback galvanic couple is connected with the pH control device, dissolved oxygen inflation sheet is connected with the gas transmission control device, and the bottom of amplifying good child-rearing device (7) in the stage casing is equipped with pneumatic mixing tank.
Described back segment adverse current leaching device (8) is outer the hot jacket of adding, two charging and discharging variable valve, dispensing plugboard and e Foerderanlage (11), and thermopair, thermopair is connected with three sections temperature control units; In the multilayer segmentation is arranged, and up/down perforation is placed stopping composition or is not placed stopping composition in segmented layer, casting resin is Xi Er ring or Raschig ring.
Described circulation feedback heating unit has two, and a circulation feedback heating unit (13) is connected by the heating jacket of variable valve with catalysis domestication device (6); Another circulation feedback heating unit (12) connects by the heating external jacket of variable valve with back segment adverse current leaching device (8), and circulation feedback heating unit (12,13) is conjuncted circulator bath heating.
Described gas transmission control device (4) aerobic gas controller and air controller, the air controller links to each other with air bacterial filter (10), and there are two adjusting control valves at air bacterial filter (10) two ends.
Flow feedback control instrument and soda acid pond are arranged in the described pH control device (5).
Described three sections temperature controllers (3) have the thermopair indicator controller, the thermopair indicator controller is connected with the thermoelectric heating temperature control instrument that the heating of good child-rearing device (7) external jacket is amplified in catalysis domestication device (6) and stage casing, also is connected with the electrically heated temperature controller that the internal heating of back segment adverse current leaching device (8) is regulated and control; Also be connected by the heating external jacket of variable valve with circulation feedback heating unit (12).
Solving the process technology scheme that its technical problem adopts is: sulfur method is: 1, will be through the thiobacillus ferrooxidant of the 9K liquid nutrient medium enrichment culture of adjustment, be directed in the leading portion electrochemical catalysis domestication device from the bottom of leading portion electrochemical catalysis domestication device, adjust the controlled variable of leading portion electrochemical catalysis domestication device then; 2, open pneumatic mixing tank (6-6) control valve air-blowing dissolved oxygen; 3, will be fed through the stage casing through catalysis nutrient solution domestication and that be rich in thiobacillus ferrooxidant and amplify in the good child-rearing device, start whole three sections temperature controls and circulation feedback heating unit, adjust controlled variable; 4, open the gas transmission control device, air is tamed device, stage casing by the air bacterial filter to electrochemical catalysis and is amplified the good child-rearing device and provide air-flow, oxygenation in the good child-rearing device is amplified in the stage casing simultaneously; 5, the potential of hydrogen in the pH control device self-centering section amplification good child-rearing device is regulated; 6, the thiobacillus ferrooxidant bacterium liquid that will amplify after the good child-rearing is squeezed into to back segment adverse current leaching device by liquid pump, the iron of thiobacillus ferrooxidant bacterium liquid self, sulphur oxidase system carry out oxidation to the sulphur in the coal of institute's desulfurization and leach, after leaching finishes, circulated in countercurrent liquid is squeezed into the sulfur recovery pond by pump, contain solubility sulfur material and the bacterium liquid deviate from, various solubility sulfurs are reduced to the recovery of sulphur precipitation, utilize in the coal, upper strata bacterium liquid flows into biological leaching device and recycles, carry out the operation of interval type cleaned coal discharge then, transport cleaned coal by dummy car or conveying belt;
The composition and the content of the 9K liquid nutrient medium in the sulfur method step 1 are: FeSO
4, 45.0 grams per liter to 44.78 grams per liters; (NH4)
2SO
4, 3.0 grams per liter to 2.5 grams per liters; MgSO
47H
2O, 0.5 grams per liter; KCl, 0.1 grams per liter; K
2HPO
4, 0.5 grams per liter; Ca (NO
3)
2, 0.01 grams per liter to 0.02 grams per liter; The proportioning of 9K liquid nutrient medium and thiobacillus ferrooxidant liquid is according to 5%～20% inoculum size (V/V) proportioning; The controlled variable of leading portion electrochemical catalysis domestication device is: externally-applied potential-500mv～-650mv, the pH value is 1.5～2.0,25 ℃～30 ℃ of temperature, time length 3～5h;
Controlled variable in the sulfur method step 3 is: the pH value of pH control device control bacterium liquid is 1.5～2.0; External control current potential-500mv～-650mv; Water cycle heating jacket temperature is 25 ℃～30 ℃; Priming color is a light green, becomes muddy after 2～3 days gradually, and color becomes little Huang, and bacterial concentration is 109/ml; Opacity strengthens in the time of 5～6 days, produces jarosite class precipitation, and bacterium liquid color further adds and is deep to orange, and bacterial concentration is 109/ml～1011/ml.
Beneficial effect: in the such scheme, electrochemical process for treating is used for the biological desulphurization process, the surface oxidation reduction that takes place under different electrochemical conditions by means of Bed for Fine Coal and pyrite reacts, make coal grain and pyrite particle surface modification, the growth metabolism of the ferrous thiobacillus of promotes oxidn is to improve sweetening effectiveness simultaneously; Add suitable volts DS or electric current at desulfurization system, can regulate and control the solubility behavior of sulfide mineral in the acidic medium, the Eh of strict control solution, the activity of desulphurase in the T.f thalline is improved, bacterial concentration increases, thereby raising desulfurization rate, after adopting the electrochemical regulating and controlling biological desulphurization for coal, the thiobacillus ferrooxidant growth cycle is contracted to 3～5 days by 8～10 days of prior art, desulfurization time contracted to 9～11 days by about 15 days, and desulfurization degree reaches 56.12%, and coal is in processing, transform, during desulfurizing and purifying in the utilization, efficiently, less energy-consumption, non-secondary pollution has reached purpose of the present invention.
Advantage of the present invention is: adopted electrochemical regulating and controlling biological desulphurization for coal method and dedicated control device, on dedicated control device, apply External Electrical Field in microorganism, strengthened thiobacillus ferrooxidant to absorption of pyrite high selectivity and biochemical action, Fe
2+Be oxidized to Fe
3+Under sour environment and biological metabolism enzyme catalysis, various low price sulphur begin to transform to high price sulphur, carry out inducing and acclimating by its physiology electrical characteristic response, in this process, corresponding biochemical reaction takes place in the organism pericentral siphon, promoted the growth metabolism of bacterium, reproduction speed is accelerated, the needed time reduced to 3～5 days by common 8～10 days when reaching identical bacterial concentration, the system response color is progressively deepened, three electrodes in the catalysis domestication device in the dedicated control device, pneumatic mixing and base condition, satisfied the environment of system requirement, stablized bacterium liquid phase pass reaction density through amplifying the good child-rearing device again, speed, the order of magnitude, acid-basicity, bacterium liquid enters the leaching device and implements circulation desulfurization purification sorting, like this according to electrochemistry, the chemical reaction regulation and control, bio-oxidation, catalysis, metabolic enzyme catalysis, domestication, effect and stable that thiobacillus ferrooxidant is adsorbed pyrite high selectivity in the coal and biochemical action has been tended towards superiority, system's desulfurization time shortens greatly and reaches ideal than high desulfurization rate; Meanwhile, pyrite surface is carried out modification, its wetting ability is strengthened, the desulfurization that is used in coal is arranged more by electrochemical action; In addition, auxiliary packings such as interpolation Xi Er ring, Raschig ring will strengthen leaching circulation desulfurization effect and raise the efficiency in the leaching circulation desulfurizing device; The present invention can adapt to the desulfurization of handling various Bed for Fine Coal and coal slime and handle, recyclable sulphur byproduct simultaneously, have structure and simple to operate, stable, processing efficiency is high, set up the advantage that the control device regulation and control are flexible, processing cost is low.
Description of drawings
Fig. 1 is a structure iron of the present invention.
Among the figure, 1, leading portion electrochemistry domestication control device; 1-1, CHI electrochemical analyser; 1-2, data storage and controller; 1-3, computer acquisition feedback system; 2, the good child-rearing control device is amplified in the stage casing; 2-1, two apparent constant pressure and flow instrument; 2-2, voltmeter; 2-3, reometer; 3, three sections temperature control units; 3-1, thermopair indicator controller; 3-2, domestication and amplification good child-rearing device chuck temperature controller; 3-3, adverse current leaching device chuck temperature controller; 4, gas transmission control device; 4-1, dissolved oxygen meter; 4-2, air controller; 5, pH control device; 5-1, flow feedback control instrument; 5-2, PH determinator; 6, leading portion electrochemical catalysis domestication device; 6-1, catalysis three electrodes; 6-2, thermopair; 6-3, charging valve; 6-4, discharging valve; 6-5, chuck outlet water control valve; 6-6, pneumatic mixing tank; 6-7, domestication heating jacket; 7, the good child-rearing device is amplified in the stage casing; 7-1, sheet two electrodes; 7-2, thermopair; 7-3, dissolved oxygen amount transmitter; 7-4, PH determination sensor; 7-5, sample cock; 7-6, stage casing bacterium liquid discharging control valve; 7-7, feed supplement valve; 7-8, pneumatic mixing tank; 7-9, chuck outlet water control valve; 8, back segment adverse current leaching device; 8-1, charging valve; 8-2, discharging valve; 8-3, dispensing plugboard; 8-4, chuck water inlet control valve; 8-5, temperature sensor; 8-6, chuck outlet water control valve; 9, sulfur recovery unit; 9-1, leaching liquid discharging valve; 9-2, sample cock; 9-3, dispensing valve; 9-4, medicament valve; 10, air bacterial filter; 10-1, the valve of giving vent to anger; 10-2, air intake valve; 11, blowing e Foerderanlage; 11-1, receiving hopper; 11-2, conveying belt; 12, circulating heater; 12-1, add the hot water flowing water Valve; 13, circulating heater; 13-1, add the hot water flowing water Valve; 14, pump system; 14-1, leaching device bacterium liquid pan feeding pump; 14-2, sulfur recovery unit discharging liquid pump.
Embodiment
Embodiment 1: agent set comprises leading portion electrochemical catalysis domestication device 6, stage casing amplification good child-rearing device 7, back segment adverse current leaching device 8; Auxiliary facility comprises that leading portion electrochemistry domestication control device 1, stage casing amplify good child-rearing control device 2, three sections temperature control units 3, circulation feedback heating unit 12, gas transmission control device 4, pH control device 5, sulfur recovery unit 9, air bacterial filter 10 and blowing e Foerderanlages 11; Leading portion electrochemical catalysis domestication device is connected with three sections temperature control units with leading portion electrochemistry domestication control device simultaneously, the stage casing is amplified the good child-rearing device and is amplified the good child-rearing control device with the stage casing simultaneously, three sections temperature control units, the gas transmission control device is connected with the pH control device, back segment adverse current leaching device is connected with sulfur recovery unit with three sections temperature control units, three sections temperature control units are by circulation feedback heating unit and leading portion electrochemical catalysis domestication device, the stage casing is amplified the good child-rearing device and is connected with back segment adverse current leaching device, leading portion electrochemical catalysis domestication device, the overcoat that good child-rearing device and back segment adverse current leaching device are amplified in the stage casing passes through pipeline, valve is connected, and the gas transmission control device amplifies good child-rearing device with leading portion electrochemical catalysis domestication device with the stage casing by air bacterial filter device and is connected.
Described leading portion electrochemical catalysis domestication device comprises electrochemistry control device and catalysis domestication device, in the electrochemistry control device, catalysis three electrodes link to each other with data-carrier store and controller with potentiometric controller, and by serial communication interface with data transmission to computer, utilize it to gather feedback system and analysis software control electrochemical parameter; In the catalysis domestication device catalysis three electrodes, thermopair 6-2 and pneumatic mixing tank 6-6 are housed, outside catalysis domestication device, three charging and discharging control valves are arranged, a water cycle heating jacket; Catalysis three electrodes of catalysis domestication device are connected with the electrochemistry control device, and thermopair is connected with three sections temperature control units, in the inside of catalysis domestication device pneumatic mixing tank are installed.
Described stage casing is amplified the good child-rearing control device and is comprised stage casing domestication control device 2 and stage casing amplification good child-rearing control device 7, and in the stage casing domestication control device 2, two apparent constant voltage/current isolators connect reference electrodes and working electrode, amplify good child-rearing device 7 to the stage casing and add volta potential; Amplify in the stage casing four charging and discharging control valves, pneumatic mixing tank, water cycle heating jacket outside the good child-rearing device 7; Amplify in the good child-rearing device 7 in stage casing amplification control device 2 and stage casing has the sheet two electrodes to be connected, soda acid supply shower nozzle is installed in the top that good child-rearing device 7 is amplified in the stage casing, the feedback galvanic couple is connected with the pH control device, dissolved oxygen inflation sheet is connected with the gas transmission control device, and the inside of amplifying good child-rearing device 7 in the stage casing is equipped with pneumatic mixing tank 7-8.
Outside the described back segment adverse current leaching device 8 hot jacket of adding, two charging and discharging variable valve are arranged, dispensing plugboard and thermopair, thermopair is connected with three sections temperature control units; In the multilayer segmentation is arranged, and up/down perforation is placed stopping composition or is not placed stopping composition in segmented layer, casting resin is Xi Er ring or Raschig ring.
Described circulation feedback heating unit has two, and a circulation feedback heating unit 13 is connected by the heating jacket of variable valve with catalysis domestication device 6; Another circulation feedback heating unit 12 connects by the heating external jacket of variable valve with back segment adverse current leaching device 8, and circulation feedback heating unit 12,13 is conjuncted circulator bath heating.
Described gas transmission control device 4 aerobic gas controllers and air controller, the air controller links to each other with air bacterial filter 10, and there are two adjusting control valves at air bacterial filter 10 two ends.
Flow feedback control instrument and soda acid pond are arranged in the described pH control device 5.
Described three sections temperature controllers 3 have the thermopair indicator controller, the thermopair indicator controller is connected with the thermoelectric heating temperature control instrument that the heating of good child-rearing device 7 external jackets is amplified in catalysis domestication device 6 and stage casing, also is connected with the electrically heated temperature controller that the internal heating of back segment adverse current leaching device 8 is regulated and control; Also be connected by the heating external jacket of variable valve with circulation feedback heating unit N.
Sulfur method is: 1, will be through the thiobacillus ferrooxidant of the 9K liquid nutrient medium enrichment culture adjusted, be directed in the leading portion electrochemical catalysis domestication device from the bottom of leading portion electrochemical catalysis domestication device, adjust the controlled variable of leading portion electrochemical catalysis domestication device then; 2, open pneumatic mixing tank 6-6 control valve air-blowing dissolved oxygen; 3, will be fed through the stage casing through catalysis nutrient solution domestication and that be rich in thiobacillus ferrooxidant and amplify in the good child-rearing device, start whole three sections temperature controls and circulation feedback heating unit, adjust controlled variable; 4, open the gas transmission control device, air is tamed device, stage casing by the air bacterial filter to electrochemical catalysis and is amplified the good child-rearing device and provide air-flow, oxygenation in the good child-rearing device is amplified in the stage casing simultaneously; 5, the potential of hydrogen in the pH control device self-centering section amplification good child-rearing device is regulated; 6, the thiobacillus ferrooxidant bacterium liquid that will amplify after the good child-rearing is squeezed into to back segment adverse current leaching device by liquid pump, the iron of thiobacillus ferrooxidant bacterium liquid self, sulphur oxidase system carry out oxidation to the sulphur in the coal of institute's desulfurization and leach, after leaching finishes, circulated in countercurrent liquid is squeezed into the sulfur recovery pond by pump, contain solubility sulfur material and the bacterium liquid deviate from, various solubility sulfurs are reduced to the recovery of sulphur precipitation, utilize in the coal, upper strata bacterium liquid flows into biological leaching device and recycles, carry out the operation of interval type cleaned coal discharge then, transport cleaned coal by dummy car or conveying belt;
The composition and the content of the 9K liquid nutrient medium in the sulfur method step 1 are: FeSO
4, 45.0 grams per liters; (NH4)
2SO
4, 3.0 grams per liters; MgSO
47H
2O, 0.5 grams per liter; KCl, 0.1 grams per liter; K
2HPO
4, 0.5 grams per liter; Ca (NO
3)
2, 0.01 grams per liter; The proportioning of 9K liquid nutrient medium and thiobacillus ferrooxidant liquid is according to 10% inoculum size (V/V) proportioning; The controlled variable of leading portion electrochemical catalysis domestication device is: externally-applied potential-500mv, and the pH value is 1.5,25 ℃ of temperature, time length 3h;
Controlled variable in the sulfur method step 3 is: the pH value of pH control device control bacterium liquid is 1.5; External control current potential-500mv; Water cycle heating jacket temperature is 25 ℃; Priming color is a light green, becomes muddy after 3 days gradually, and color becomes little Huang, and bacterial concentration is 10
9Individual/ml; Opacity strengthens in the time of 5～6 days, produces jarosite class precipitation, and bacterium liquid color further adds and is deep to orange, and bacterial concentration is 10
9Individual/ml～10
11Individual/ml.
Start the circulation feedback heating unit 12,13 of electrochemical regulating and controlling biological desulphurization for coal system and device, open the input and output control valve, hot water input catalysis domestication device 6, the stage casing that will meet the temperature condition requirement amplify good child-rearing device 7 and after the water-bath chuck of the section of having no progeny adverse current leaching device 8, and, satisfy system requirements by the temperature in three sections temperature control units, 3 regulation and control its each devices.Catalysis domestication device 6 inserts bacterium liquid and substrate (nutrient solution), catalysis three combination of electrodes and thermopair are installed, open the built-in air controller of gas transmission control device 4, the air controller links to each other with air bacterial filter 10, enable air bacterial filter 10, and open two adjusting control valves and be communicated with pneumatic mixing tank, catalysis domestication device 6 is charged into sterile air, open buffering unloading control valve balance internal pressure then; Open setting up electrolyzer controller, data storage and controlling serial communication interface and computer acquisition feedback CHI601b software system of leading portion electrochemistry control device 1, start working, because air dissolved oxygen and T.f. effect are down with Fe in the substrate liquid
2+Change into Fe
3+Consume H simultaneously
+, reactional equation is as follows:
4Fe
2++O
2+4H
+→4Fe
3++2H
2O……………………(1)
The environment pH value raises as a result, Fe
3+With oxygen sulphur is at a low price partly changed into elemental sulfur and than high state sulphur:
S
X→S
O+S
Y………………………………………(2)
Part S
OAnd S
X, S
YUnder T.f. bacterium catalysed oxidn, generate sulfuric acid attitude high price sulphur again:
S
O、S
X、S
Y→SO
4 2-+H
++…………………………(3)
The H that produces
+Make that again acidity raises, pH value descends, so this process is not only to consume acid but also produce acid, works as Fe
2+Change into Fe
3+, accumulation reaches certain value, and ferric sulphate just shows the intensive oxidisability, and reductibility compares S in the system
O, S
YStrong ion or compound take the lead in being able to oxidation, and reactional equation is as follows:
M
a、X+Fe
3+→M
b+Y+Fe
2+……………………(4)
The ferrous sulfate of so new generation repeats the reaction of equation (1) under the T.f. effect, pH value raises again, and continue again (2) (3); Because reductibility compares S in the system
O, S
YStrong ion or compound are finished by the ferric sulphate oxidation, and the sulphur at a low price of various forms all changes into sulfuric acid and sulphate form, and reactional equation is as follows:
S
X、S
O、S
Y+Fe
3+→SO
4 2+H
++…………………(5)
Bacterial classification is through the preliminary adaptability domestication of leading portion in the catalysis domestication device 6, after proterties is stable, open control valve and change bacterium liquid over to stage casing amplification good child-rearing device 7, establish sheet two electrodes, thermopair, dissolved oxygen aerator, soda acid supply shower nozzle and transmitter, three input and output material control valves of peripheral hardware, pneumatic mixed plate, water cycle heating jacket in the stage casing amplification good child-rearing device 7.Open control valve and charge into sterile air to pneumatic mixing tank by air bacterial filter 10, agitation system, realize fully turbulent flow, the stage casing amplification control device 2 that links to each other with stage casing amplification good child-rearing device 7 sets up system selector switch, voltmeter and reometers such as two apparent constant pressure and flows, simulation pond, reference separately, after the unlatching, fill oxygen to dissolved oxygen inflation sheet by the oxygen controller in the gas transmission control device 4, like this external electrical field that good child-rearing device 7 continues to apply the requirement of catalysis domestication device, stable and optimization bacterium performance and desulphurization system physical and chemical indexes are amplified in the stage casing; Open control valve, liquid pump M then
1And variable valve, satisfactory desulfurization bacterium liquid enters thermoelectric heating temperature control instrument regulation and control combination thermoelectric heater and thermopair in 8, three sections temperature control units 3 of back segment adverse current leaching device, with regulation and control adverse current leaching device 8 internal temperatures, sets up two discrepancy variable valve, liquid pump M
2All open with variable valve, supernatant liquor flows back to adverse current leaching device after the desulfurization, and the unimpeded circulation of adverse current leaching system is when getting lixivium sample check and analysis sulphur content through the sampling valve exit and meet the requirements, open plate at the bottom of the discharging, cleaned coal is put into e Foerderanlage 11 outputs through the funnel that connects material.
Described catalysis domestication device 6 can use separately as the bacteria domestication device, also can amplify good child-rearing device 7 with the stage casing and unite use, makes scale-up step by step.
Back segment adverse current leaching device 8 and set up also and can make the post lixiviation apparatus separately, or use as flotation column.The adding of adverse current leaching device H filler can be adjusted accordingly according to handling sample, can be single filler or compounded mix, and it mainly acts on is to carry out biological fixnig, or provides nutrition for bacterium.
The invention provides the electrochemistry-biological duplex regulate and control method and the relative unit of coal desulfurization, effective to coal desulfurization, the efficient height, experiment shows: to the desulfurization of Bed for Fine Coal, especially removing of sulphur obtained desired result in the superfine beans, and energy consumption is low, non-secondary pollution, economic environmental protection has popularizing application prospect preferably.
Embodiment 2: the composition and the content of the 9K liquid nutrient medium in the sulfur method step 1 are: FeSO
4, 44.78 grams per liters; (NH4)
2SO
4, 2.5 grams per liters; MgSO
47H
2O, 0.5 grams per liter; KCl, 0.1 grams per liter; K
2HPO
4, 0.5 grams per liter; Ca (NO
3)
2, 0.02 grams per liter; The proportioning of 9K liquid nutrient medium and thiobacillus ferrooxidant liquid is according to 10% inoculum size (V/V) proportioning; The controlled variable of leading portion electrochemical catalysis domestication device is: externally-applied potential-650mv, and the pH value is 2.0,30 ℃ of temperature, time length 5h;
Controlled variable in the sulfur method step 3 is: the pH value of pH control device control bacterium liquid is 2.0; External control current potential-650mv; Water cycle heating jacket temperature is 30 ℃; Priming color is a light green, becomes muddy after 2 days gradually, and color becomes little Huang, and bacterial concentration is 10
9Individual/ml; Opacity strengthens in the time of 5～6 days, produces jarosite class precipitation, and bacterium liquid color further adds and is deep to orange, and bacterial concentration is 10
9Individual/ml～10
11Individual/ml.Other and embodiment 1 omit together.
Embodiment 3: the composition and the content of the 9K liquid nutrient medium in the sulfur method step 1 are: FeSO
4, 44.85 grams per liters; (NH4)
2SO
4, 2.75 grams per liters; MgSO
47H
2O, 0.5 grams per liter; KCl, 0.1 grams per liter; K
2HPO
4, 0.5 grams per liter; Ca (NO
3)
2, 0.015 grams per liter; The proportioning of 9K liquid nutrient medium and thiobacillus ferrooxidant liquid is according to 10% inoculum size (V/V) proportioning; The controlled variable of leading portion electrochemical catalysis domestication device is: externally-applied potential-600mv, and the pH value is 1.8,27 ℃ of temperature, time length 4h;
Controlled variable in the sulfur method step 3 is: the pH value of pH control device control bacterium liquid is 1.8; External control current potential-590mv; Water cycle heating jacket temperature is 28 ℃; Priming color is a light green, becomes muddy after 2 days gradually, and color becomes little Huang, and bacterial concentration is 10
9Individual/ml; Opacity strengthens in the time of 5～6 days, produces jarosite class precipitation, and bacterium liquid color further adds and is deep to orange, and bacterial concentration is 10
9Individual/ml～10
11Individual/ml.Other and embodiment 1 omit together.
Claims (9)
1. electrochemical regulating and controlling biological desulphurization for coal method is characterized in that:
Adopt the device of electrochemical regulating and controlling biological desulphurization for coal method, agent set comprises leading portion electrochemical catalysis domestication device, stage casing amplification good child-rearing device, back segment adverse current leaching device; Auxiliary facility comprises that the good child-rearing control device is amplified in leading portion electrochemistry domestication control device, stage casing, heating unit, gas transmission control device, pH control device, sulfur recovery unit and air bacterial filter devices are fed back in three sections temperature control units, circulations; Leading portion electrochemical catalysis domestication device is connected with three sections temperature control units with leading portion electrochemistry domestication control device simultaneously, the stage casing is amplified the good child-rearing device and is amplified the good child-rearing control device with the stage casing simultaneously, three sections temperature control units, the gas transmission control device is connected with the pH control device, back segment adverse current leaching device is connected with sulfur recovery unit with three sections temperature control units, three sections temperature control units are by circulation feedback heating unit and leading portion electrochemical catalysis domestication device, the stage casing is amplified the good child-rearing device and is connected with back segment adverse current leaching device, leading portion electrochemical catalysis domestication device, the overcoat that good child-rearing device and back segment adverse current leaching device are amplified in the stage casing passes through pipeline, valve is connected, the gas transmission control device amplifies good child-rearing device with leading portion electrochemical catalysis domestication device with the stage casing by air bacterial filter device and is connected, described leading portion electrochemical catalysis domestication device comprises electrochemistry control device and catalysis domestication device, in the electrochemistry control device (1), catalysis electrode links to each other with data-carrier store and controller with potentiometric controller, and by serial communication interface with data transmission to computer, utilize it to gather feedback system and analysis software control electrochemical parameter; In the catalysis domestication device (6) catalysis three electrodes, thermopair (6-2) and pneumatic mixing tank are housed, outside catalysis domestication device, three charging and discharging control valves are arranged, a water cycle heating jacket; Catalysis three electrodes of catalysis domestication device are connected with the electrochemistry control device, thermopair is connected with three sections temperature control units, inside at catalysis domestication device (6) is equipped with pneumatic mixing tank, described stage casing is amplified the good child-rearing control device and is comprised stage casing domestication control device (2) and stage casing amplification good child-rearing control device (7), in the stage casing domestication control device (2), two apparent constant voltage/current isolators connect reference electrode and working electrode, amplify good child-rearing device (7) to the stage casing and add volta potential; Amplify in the stage casing four charging and discharging control valves, pneumatic mixing tank, water cycle heating jacket outside the good child-rearing device (7); Amplify in the good child-rearing device (7) in stage casing amplification control device (2) and stage casing has the sheet two electrodes to be connected, soda acid supply shower nozzle is installed in the top that good child-rearing device (7) is amplified in the stage casing, the feedback galvanic couple is connected with the pH control device, dissolved oxygen inflation sheet is connected with the gas transmission control device, the bottom of amplifying good child-rearing device (7) in the stage casing is equipped with pneumatic mixing tank, described back segment adverse current leaching device (8) is outer the hot jacket of adding, two charging and discharging variable valve, dispensing plugboard and thermopair, and thermopair is connected with three sections temperature control units; In the multilayer segmentation is arranged, and up/down perforation is placed stopping composition or is not placed stopping composition in segmented layer, casting resin is a Raschig ring,
Sulfur method is: 1, will be through the thiobacillus ferrooxidant of the 9K liquid nutrient medium enrichment culture adjusted, be directed in the leading portion electrochemical catalysis domestication device from the bottom of leading portion electrochemical catalysis domestication device, adjust the controlled variable of leading portion electrochemical catalysis domestication device then; 2, open pneumatic mixing tank control valve air-blowing dissolved oxygen; 3, will be fed through the stage casing through catalysis nutrient solution domestication and that be rich in thiobacillus ferrooxidant and amplify in the good child-rearing device, start whole three sections temperature controls and circulation feedback heating unit, adjust controlled variable; 4, open the gas transmission control device, air is tamed device, stage casing by the air bacterial filter to electrochemical catalysis and is amplified the good child-rearing device and provide air-flow, oxygenation in the good child-rearing device is amplified in the stage casing simultaneously; 5, the potential of hydrogen in the pH control device self-centering section amplification good child-rearing device is regulated; 6, the thiobacillus ferrooxidant bacterium liquid that will amplify after the good child-rearing is squeezed into to back segment adverse current leaching device by liquid pump, the iron of thiobacillus ferrooxidant bacterium liquid self, sulphur oxidase system carry out oxidation to the sulphur in the coal of institute's desulfurization and leach, after leaching finishes, circulated in countercurrent liquid is squeezed into the sulfur recovery pond by pump, contain solubility sulfur material and the bacterium liquid deviate from, various solubility sulfurs are reduced to the recovery of sulphur precipitation, utilize in the coal, upper strata bacterium liquid flows into biological leaching device and recycles, carry out the operation of interval type cleaned coal discharge then, transport cleaned coal by dummy car or conveying belt;
The composition and the content of the 9K liquid nutrient medium in the sulfur method step 1 are: FeSO
4, 45.0 grams per liter to 44.78 grams per liters; (NH
4)
2SO
4, 3.0 grams per liter to 2.5 grams per liters; MgSO
47H
2O, 0.5 grams per liter; KCl, 0.1 grams per liter; K
2HPO
4, 0.5 grams per liter; Ca (NO
3)
2, 0.01 grams per liter to 0.02 grams per liter; The proportioning of 9K liquid nutrient medium and thiobacillus ferrooxidant liquid is according to 10% inoculum size (V/V) proportioning; The controlled variable of leading portion electrochemical catalysis domestication device is: externally-applied potential-500mv～-650mv, the pH value is 1.5～2.0,25 ℃～30 ℃ of temperature, time length 3～5h;
Controlled variable in the sulfur method step 3 is: the pH value of pH control device control bacterium liquid is 1.5～2.0; External control current potential-500mv～-650mv; Water cycle heating jacket temperature is 25 ℃～30 ℃; Priming color is a light green, becomes muddy after 2～3 days gradually, and color becomes little Huang, and bacterial concentration is 10
9Individual/ml; Opacity strengthens in the time of 5～6 days, produces jarosite class precipitation, and bacterium liquid color further adds and is deep to orange, and bacterial concentration is 10
9Individual/ml～10
11Individual/ml.
2. device of realizing electrochemical regulating and controlling biological desulphurization for coal method is characterized in that: agent set comprises that leading portion electrochemical catalysis domestication device, stage casing amplify good child-rearing device, back segment adverse current leaching device; Auxiliary facility comprises that the good child-rearing control device is amplified in leading portion electrochemistry domestication control device, stage casing, heating unit, gas transmission control device, pH control device, sulfur recovery unit and air bacterial filter devices are fed back in three sections temperature control units, circulations; Leading portion electrochemical catalysis domestication device is connected with three sections temperature control units with leading portion electrochemistry domestication control device simultaneously, the stage casing is amplified the good child-rearing device and is amplified the good child-rearing control device with the stage casing simultaneously, three sections temperature control units, the gas transmission control device is connected with the pH control device, back segment adverse current leaching device is connected with sulfur recovery unit with three sections temperature control units, three sections temperature control units are by circulation feedback heating unit and leading portion electrochemical catalysis domestication device, the stage casing is amplified the good child-rearing device and is connected with back segment adverse current leaching device, leading portion electrochemical catalysis domestication device, the overcoat that good child-rearing device and back segment adverse current leaching device are amplified in the stage casing passes through pipeline, valve is connected, and the gas transmission control device amplifies good child-rearing device with leading portion electrochemical catalysis domestication device with the stage casing by air bacterial filter device and is connected.
3. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2, it is characterized in that: described leading portion electrochemical catalysis domestication device comprises electrochemistry control device and catalysis domestication device, in the electrochemistry control device (1), catalysis electrode links to each other with data-carrier store and controller with potentiometric controller, and by serial communication interface with data transmission to computer, utilize it to gather feedback system and analysis software control electrochemical parameter; In the catalysis domestication device (6) catalysis three electrodes, thermopair (6-2) and pneumatic mixing tank are housed, outside catalysis domestication device, three charging and discharging control valves are arranged, a water cycle heating jacket; Catalysis three electrodes of catalysis domestication device are connected with the electrochemistry control device, and thermopair is connected with three sections temperature control units, in the inside of catalysis domestication device (6) pneumatic mixing tank is installed.
4. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2, it is characterized in that: described stage casing is amplified the good child-rearing control device and is comprised stage casing domestication control device (2) and stage casing amplification good child-rearing control device (7), in the stage casing domestication control device (2), two apparent constant voltage/current isolators connect reference electrode and working electrode, amplify good child-rearing device (7) to the stage casing and add volta potential; Amplify in the stage casing four charging and discharging control valves, pneumatic mixing tank, water cycle heating jacket outside the good child-rearing device (7); Amplify in the good child-rearing device (7) in stage casing amplification control device (2) and stage casing has the sheet two electrodes to be connected, soda acid supply shower nozzle is installed in the top that good child-rearing device (7) is amplified in the stage casing, the feedback galvanic couple is connected with the pH control device, dissolved oxygen inflation sheet is connected with the gas transmission control device, and the bottom of amplifying good child-rearing device (7) in the stage casing is equipped with pneumatic mixing tank.
5. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2, it is characterized in that: the hot jacket of adding, two charging and discharging variable valve are arranged outside the described back segment adverse current leaching device (8), dispensing plugboard and thermopair, thermopair is connected with three sections temperature control units; In the multilayer segmentation is arranged, and up/down perforation is placed stopping composition or is not placed stopping composition in segmented layer, casting resin is a Raschig ring.
6. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2 is characterized in that: described circulation feedback heating unit has two, and a circulation feedback heating unit (13) is connected by the heating jacket of variable valve with catalysis domestication device (6); Another circulation feedback heating unit (12) connects by the heating external jacket of variable valve with back segment adverse current leaching device (8), and circulation feedback heating unit (12,13) is conjuncted circulator bath heating.
7. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2, it is characterized in that: described gas transmission control device (4) aerobic gas controller and air controller, the air controller links to each other with air bacterial filter (10), and there are two adjusting control valves at air bacterial filter (10) two ends.
8. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2 is characterized in that: flow feedback control instrument and soda acid pond are arranged in the described pH control device (5).
9. the device of electrochemical regulating and controlling biological desulphurization for coal according to claim 2, it is characterized in that: described three sections temperature control units (3) have the thermopair indicator controller, the thermopair indicator controller is connected with the thermoelectric heating temperature control instrument that the heating of good child-rearing device (7) external jacket is amplified in catalysis domestication device (6) and stage casing, also is connected with the electrically heated temperature controller that the internal heating of back segment adverse current leaching device (8) is regulated and control; Also be connected by the heating external jacket of variable valve with circulation feedback heating unit (12).
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| CN101899351A (en) * | 2009-05-25 | 2010-12-01 | 山西潞安环保能源开发股份有限公司 | Method for desulfurization of coal by electrochemical catalytic oxidation |
| CN104803488A (en) * | 2015-04-28 | 2015-07-29 | 北京盈和瑞环保工程有限公司 | System for controlling automatic addition of desulfurated microorganism nutrient solution |
| CN104931547B (en) * | 2015-06-30 | 2017-10-10 | 中国矿业大学 | A kind of responding microwave attribute testing analysis method of sulphur coal and sulfur-bearing model compound |
| CN105524672A (en) * | 2016-01-28 | 2016-04-27 | 赛景波 | Production method of environment-friendly enzyme solution for coal |
| CN108359507A (en) * | 2018-03-01 | 2018-08-03 | 王号德 | A kind of method of organic sulfur compound in removing bituminous coal |
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