CN108663405A - A kind of Oxygen Bomb Combustion quickly measures the detection method of chlorine content in coal - Google Patents

A kind of Oxygen Bomb Combustion quickly measures the detection method of chlorine content in coal Download PDF

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CN108663405A
CN108663405A CN201810628140.1A CN201810628140A CN108663405A CN 108663405 A CN108663405 A CN 108663405A CN 201810628140 A CN201810628140 A CN 201810628140A CN 108663405 A CN108663405 A CN 108663405A
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oxygen bomb
coal
people
beaker
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苏龙
邓月明
杨艳
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Hunan Normal University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N25/20Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/22Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract

The present invention discloses the detection method that a kind of Oxygen Bomb Combustion quickly measures chlorine content in coal, and step is:1. the combustion boat equipped with sample is put on oxygen bomb frame;2. sodium hydroxide solution is added in oxygen bomb, oxygen is injected into oxygen bomb;3. connecting ignitor;4. after Oxygen Bomb Combustion, collecting test solution in beaker;5. the solution such as sodium hydroxide are added, filtered with qualitative filter paper, places half an hour progress constant-current titration measurement;6. test solution is transferred to beaker, it is put into stirrer, electrode is inserted into, starts blender;7. the beaker for filling blank solution is placed on titration platform, the silver nitrate standard solution of drop people's amount is had determined that with the speed drop people of 0.03mL/s, records silver nitrate standard solution dosage;8. the beaker for filling sample solution is placed on titration platform.People's silver nitrate standard solution is first dripped with the speed of 0.05mL/s, when close to the terminal current potential demarcated, is titrated with 0.02mL/s speed until reaching the terminal current potential of calibration.Stirring 1min writes down silver nitrate standard solution and people is added to measure;9. the calculating of chlorine content in coal.

Description

A kind of Oxygen Bomb Combustion quickly measures the detection method of chlorine content in coal
Technical field
The invention belongs to chemical analysis detection technique fields, and in particular to a kind of Oxygen Bomb Combustion quickly measures chlorine content in coal Detection method.
Background technology
Chlorine is a kind of nonmetalloid, is located at periodic table of elements period 3 V Group IIA, belongs to one of halogen family.Chlorine is normal It is yellow green gas under normal temperature and pressure, chemical property is very active, has toxicity.Chlorine is widely present in nature in the form of compound state It is also significant to the physiological activity of human body in boundary.Chlorine is yellow green gas, and density ratio air is big (3.214g/L), - 101.0 DEG C of fusing point, -34.4 DEG C of boiling point have strong impulse smell.This also carrys out more serious ask to environment and economy-zone Topic.So as to develop the detection method of chlorine content in coal, further to control content of Cl element in coal and reduce harmful gas Body discharges.
At present for the detection of chlorine content in coal, the country is generally measured using high-temperature combustion hydrolytic method, and this method can be with It preferably adsorbs the chlorine element in producing coal and more accurately measures chlorinity result.In pyrohydrolysis, coal sample and quartz Sand is mixed and burned, and is transferred in condensed water in a chloride-form, in this process, chlorine cannot adsorb therewith completely in coal, just quilt Absorbing chlorine may be gone back by the absorption of the substances such as coal ash again, in addition vapor evaporation capacity and oxygen flow can blow away compared with small coal Sample is affected to test result, is affected to test result.Another problem be exactly experimental period it is longer, in high-temperature water Combustion hydrolytic 5min is respectively carried out to 300 DEG C, 600 DEG C, 800 DEG C of warm areas in solution preocess, high-temperature region of then making a gift to someone again (1100 DEG C of grades with On) combustion hydrolytic 15min, 30min, testing efficiency are relatively low in total.High-temperature combustion hydrolytic process cannot be handled in coal sample completely Chlorinity, and experimental period is tediously long, the final accuracy and efficiency for influencing measurement result.
Invention content
In order to solve the above technical problems, the present invention provides the detection sides that a kind of Oxygen Bomb Combustion quickly measures chlorine content in coal Method, it is high that content of Cl element measures accurate and testing efficiency.
In order to achieve the above objectives, technical solution of the present invention is as follows:A kind of Oxygen Bomb Combustion quickly measures the inspection of chlorine content in coal Survey method, feature include the following steps:
Oxygen bomb configuration condition:Halogen resistant element is fluorinated oxygen bomb, and oxygen bomb decomposing system is marked according to DIN51577, DIN/EN14582 Standard makes sample in the oxygen bomb of closed oxygenation, fully burns, decomposites required element or ingredient.And oxygen bomb is by special The catalyst combination of material, refined stainless steel alloy and automatic regeneration forms, and can prevent oxygen bomb from exploding and hurting operator, energy Enough ensure that digestion process can be smoothed out, so that sample is reached resolution effect well, can more importantly prevent oxygen bomb in sample Chlorine element have suction-operated, once oxygen bomb and chlorine element chemically reactive, then can influence measurement result.
Reagent configures
A. chlorination sodium standard solution, the top grade sodium chloride for weighing 0.6596g are put into beaker and are dissolved in a small amount of water, be washed with water into In 2000mL volumetric flasks and it is diluted to scale, is shaken up, is stored;
B. silver nitrate standard solution (0.01411mol/L), the top grade silver nitrate for weighing 2.3969g are put into beaker and are dissolved in a small amount of In water, it is washed with water in 1000mL volumetric flasks and is diluted to scale, is shaken up, stored;
C. the sodium hydroxide solution of 10g/L is configured, the top grade sodium hydroxide for weighing 1g is dissolved in the water of 100mL;
D. bromocresol green indicator (10g/L) is weighed in 1g bromocresol green 100mL ethyl alcohol;
The 1 volume top pure grade concentrated sulfuric acid is slowly added in 23 volume of water, mixing by e. sulfuric acid solution;
The top pure grade potassium nitrate of sufficient amount is dissolved in a small amount of water by f. potassium nitrate saturated solution, continuously adds potassium nitrate until not It is redissolved, and with the presence of a certain amount of solid nitric acid potassium in solution.
Sampling:Coal sample is dried in air, be sieved 0.2mm.Accurately weighing 1.000g (± 0.0002) coal sample is placed in combustion It burns in ware.
The testing conditions of potentiometric titrimeter:Millivoltmeter;Digital precision 0.1mV;Magnetic stirring apparatus, mixing speed 500r/min and continuously adjustable;Buret, 10mL;Salt bridge dissolves by heating 10g potassium nitrate and 1.5g agar powders and 50mL distilled water In, slightly cold rear injection U-shaped glass tube;Indicator electrode, the fine silver silk of diameter 3mm;Reference electrode, silver-silver chloride reference electrode (can Self-control can purchase).
Test method
Combustion boat is put on oxygen bomb frame by the first step, connects ignition wire;
10mL sodium hydroxide solutions are added in oxygen bomb, carefully tighten oxygen bomb lid for second step, and oxygen is injected into oxygen bomb to 2.8- 3.0MPa simultaneously keeps 15s or more;
Third walks, and connects ignitor, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, Oxygen Bomb Combustion terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder (in cylinder Have several coal sample burnings insufficient, then test calcellation) collecting whole test solutions, (control test solution must not be higher than in the beaker of 100mL 100mL), 85mL or so is usually taken;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulphur Acid solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, It shakes up, places half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers by the 6th step, is put into stirrer, is inserted into silver-silver chloride reference electrode and instruction Electrode starts blender;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Drop people has determined that the silver nitrate standard solution of drop people's amount, records potential value at this time, and the silver nitrate standard solution recorded at this time is used Amount;
The beaker for filling sample solution is placed on titration platform by the 8th step.People's silver nitrate standard is first dripped with the speed of 0.05mL/s Solution, the millivolt number that observation millivoltmeter is shown are titrated with 0.02mL/s speed when close to the terminal current potential demarcated until reaching mark Fixed terminal current potential.Silver nitrate standard solution adds people to measure under stirring 1min postscripts;
9th step, the calculating of chlorine content in coal
Cl-air-dried sample chlorinity, in terms of mass fraction (%);The silver nitrate standard solution of V1-calibration terminal current potential Dosage, unit are milliliter (mL);The silver nitrate standard solution dosage of V2-titration coal sample solution, unit are milliliter (mL);C-nitre The concentration of sour silver standard solution, unit are mM every milliliter (mmol/mL);MM quality of M-chlorine, in terms of 0.03545, Unit is gram every mM (g/mmol);M-air-dried sample quality, unit are gram (g).
Compared with prior art, detection method preferably will in coal inhale chlorine it is attached out, experimental period can shorten 15min facilitates detection, and testing efficiency is high, and detection method is simple and practicable, reaches 97%-99% using the rate of recovery of the method.
Description of the drawings
Fig. 1 is Oxygen Bomb Combustion apparatus structure schematic diagram used in detection method.
Fig. 2 is potentiometric titrimeter structural schematic diagram used in detection method.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is further described.
The present invention design a kind of Oxygen Bomb Combustion quickly measure chlorine content in coal detection method (abbreviation detection method, referring to Fig. 1,2), is as follows:
Processed coal sample is poured into the combustion boat in oxygen bomb 2, then oxygen bomb is put into protective device 4 by the first step, anti-block Bullet explodes and hurts operator, connection igniter 3 and protective device 4;
Second step, in oxygen bomb be added 10mL sodium hydroxide solutions, carefully tighten oxygen bomb lid, into oxygen bomb 2 inject oxygen 1 to 2.8-3.0MPa simultaneously keeps 15s or more;
Third walks, and presses ignitor 5, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, the burning of oxygen bomb 2 terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder (in cylinder Have several coal sample burnings insufficient, then test calcellation) collecting whole test solutions, (control test solution must not be higher than in the beaker of 100mL 100mL), 85mL or so is usually taken;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulphur Acid solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, It shakes up, places half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers 3 by the 6th step, is put into stirrer 2, is inserted into 5 He of silver-silver chloride reference electrode Indicator electrode 4 starts blender 6;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Buret 7 drips the silver nitrate standard solution that people has determined that drop people's amount, observes millivoltmeter 1, records potential value at this time, record is at this time Silver nitrate standard solution dosage;
The beaker 3 for filling sample solution is placed on titration platform by the 8th step.People's nitre is first dripped with the speed buret 7 of 0.05mL/s Acid silver standard solution, the millivolt number that observation millivoltmeter 1 is shown are titrated when close to the terminal current potential demarcated with 0.02mL/s speed Until reaching the terminal current potential of calibration.Silver nitrate standard solution adds people to measure under stirring 1min postscripts.
9th step, calculates chlorine content in coal.
Embodiment 1
The chlorinity in mark coal GBW11118a is detected with detection method and device.
The first step weighs the coal sample of 0.998g, and processed coal sample is poured into the combustion boat in oxygen bomb 2, then by oxygen bomb It is put into protective device 4, prevents oxygen bomb from exploding and hurting operator, connection igniter 3 and protective device 4;
Second step, in oxygen bomb be added 10mL sodium hydroxide solutions, carefully tighten oxygen bomb lid, into oxygen bomb 2 inject oxygen 1 to 2.8-3.0MPa simultaneously keeps 15s or more;
Third walks, and presses ignitor 5, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, the burning of oxygen bomb 2 terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder (in cylinder Have several coal sample burnings insufficient, then test calcellation) collecting whole test solutions, (control test solution must not be higher than in the beaker of 100mL 100mL), 85mL or so is usually taken;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulphur Acid solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, It shakes up, places half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers 3 by the 6th step, is put into stirrer 2, is inserted into 5 He of silver-silver chloride reference electrode Indicator electrode 4 starts blender 6;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Buret 7 drips the silver nitrate standard solution that people has determined that drop people's amount, observes millivoltmeter 1, records potential value at this time, record is at this time Silver nitrate standard solution dosage;
The beaker 3 for filling sample solution is placed on titration platform by the 8th step.People's nitre is first dripped with the speed buret 7 of 0.05mL/s Acid silver standard solution, the millivolt number that observation millivoltmeter 1 is shown are titrated when close to the terminal current potential demarcated with 0.02mL/s speed Until reaching the terminal current potential of calibration.Silver nitrate standard solution adds people to measure under stirring 1min postscripts.
9th step, calculates chlorine content in coal.
Embodiment 2
The chlorinity in mark coal GBW11119a is detected with detection method and device.
The first step weighs the coal sample of 0.999g, and processed coal sample is poured into the combustion boat in oxygen bomb 2, then by oxygen bomb It is put into protective device 4, prevents oxygen bomb from exploding and hurting operator, connection igniter 3 and protective device 4;
Second step, in oxygen bomb be added 10mL sodium hydroxide solutions, carefully tighten oxygen bomb lid, into oxygen bomb 2 inject oxygen 1 to 2.8-3.0MPa simultaneously keeps 15s or more;
Third walks, and presses ignitor 5, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, the burning of oxygen bomb 2 terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder (in cylinder Have several coal sample burnings insufficient, then test calcellation) collecting whole test solutions, (control test solution must not be higher than in the beaker of 100mL 100mL), 85mL or so is usually taken;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulphur Acid solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, It shakes up, places half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers 3 by the 6th step, is put into stirrer 2, is inserted into 5 He of silver-silver chloride reference electrode Indicator electrode 4 starts blender 6;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Buret 7 drips the silver nitrate standard solution that people has determined that drop people's amount, observes millivoltmeter 1, records potential value at this time, record is at this time Silver nitrate standard solution dosage;
The beaker 3 for filling sample solution is placed on titration platform by the 8th step.People's nitre is first dripped with the speed buret 7 of 0.05mL/s Acid silver standard solution, the millivolt number that observation millivoltmeter 1 is shown are titrated when close to the terminal current potential demarcated with 0.02mL/s speed Until reaching the terminal current potential of calibration.Silver nitrate standard solution adds people to measure under stirring 1min postscripts.
9th step, calculates chlorine content in coal.
Embodiment 3
The chlorinity in mark coal GBW11120a is detected with detection method and device.
The first step weighs the coal sample of 1.002g, and processed coal sample is poured into the combustion boat in oxygen bomb 2, then by oxygen bomb It is put into protective device 4, prevents oxygen bomb from exploding and hurting operator, connection igniter 3 and protective device 4;
Second step, in oxygen bomb be added 10mL sodium hydroxide solutions, carefully tighten oxygen bomb lid, into oxygen bomb 2 inject oxygen 1 to 2.8-3.0MPa simultaneously keeps 15s or more;
Third walks, and presses ignitor 5, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, the burning of oxygen bomb 2 terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder (in cylinder Have several coal sample burnings insufficient, then test calcellation) collecting whole test solutions, (control test solution must not be higher than in the beaker of 100mL 100mL), 85mL or so is usually taken;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulphur Acid solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, It shakes up, places half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers 3 by the 6th step, is put into stirrer 2, is inserted into 5 He of silver-silver chloride reference electrode Indicator electrode 4 starts blender 6;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Buret 7 drips the silver nitrate standard solution that people has determined that drop people's amount, observes millivoltmeter 1, records potential value at this time, record is at this time Silver nitrate standard solution dosage;
The beaker 3 for filling sample solution is placed on titration platform by the 8th step.People's nitre is first dripped with the speed buret 7 of 0.05mL/s Acid silver standard solution, the millivolt number that observation millivoltmeter 1 is shown are titrated when close to the terminal current potential demarcated with 0.02mL/s speed Until reaching the terminal current potential of calibration.Silver nitrate standard solution adds people to measure under stirring 1min postscripts.
9th step, calculates chlorine content in coal.

Claims (1)

1. a kind of Oxygen Bomb Combustion quickly measures the detection method of chlorine content in coal, it is as follows:
Combustion boat is put on oxygen bomb frame by the first step, connects ignition wire;
10mL sodium hydroxide solutions are added in oxygen bomb, carefully tighten oxygen bomb lid for second step, and oxygen is injected into oxygen bomb to 2.8- 3.0MPa simultaneously keeps 15s or more;
Third walks, and connects ignitor, and the igniting that is powered, burning, burning time must not be less than 15min;
4th step, Oxygen Bomb Combustion terminate postcooling 15min, carefully open vent valve, are decompressed to normal pressure, open cylinder(In cylinder There are several coal sample burnings insufficient, then tests calcellation)Whole test solutions are collected in the beaker of 100mL(Control test solution must not be higher than 100mL), usually take 85mL or so;
5th step is added 3 drop bromocresol green indicator, is neutralized to indicator with 5% sodium hydroxide and just become blue, add 1mL sulfuric acid Solution, 3mL potassium nitrate saturated solution and 5mL chlorination sodium standard solutions filter test solution with qualitative filter paper, determine solution in scale, shake It is even, place half an hour progress constant-current titration measurement;
The test solution of preparation is transferred in 100mL beakers by the 6th step, is put into stirrer, is inserted into silver-silver chloride reference electrode and instruction Electrode starts blender;
7th step, the calibration of titration end-point current potential:The beaker for filling blank solution is placed on titration platform, with the speed of 0.03mL/s Drop people has determined that the silver nitrate standard solution of drop people's amount, records potential value at this time, and the silver nitrate standard solution recorded at this time is used Amount;
The beaker for filling sample solution is placed on titration platform by the 8th step, first drips people's silver nitrate standard with the speed of 0.05mL/s Solution, the millivolt number that observation millivoltmeter is shown are titrated with 0.02mL/s speed when close to the terminal current potential demarcated until reaching mark Fixed terminal current potential stirs silver nitrate standard solution under 1min postscripts and people is added to measure;
9th step, the calculating of chlorine content in coal.
CN201810628140.1A 2018-06-19 2018-06-19 A kind of Oxygen Bomb Combustion quickly measures the detection method of chlorine content in coal Pending CN108663405A (en)

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