CN114414722B - Method for measuring carbon dioxide content in phosphorite - Google Patents
Method for measuring carbon dioxide content in phosphorite Download PDFInfo
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- CN114414722B CN114414722B CN202210056558.6A CN202210056558A CN114414722B CN 114414722 B CN114414722 B CN 114414722B CN 202210056558 A CN202210056558 A CN 202210056558A CN 114414722 B CN114414722 B CN 114414722B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Abstract
The invention discloses a method for measuring the carbon dioxide content in phosphorite, which can realize monitoring of the reaction starting time, the reaction temperature and the reaction speed of reactants in a reaction bottle by utilizing the cooperation of a heating mechanism and a thermometer, and realize the rapid cooling of gas by injecting circulating cooling water into a cooling cavity formed by the reaction bottle and a cover body; the method can accurately control experimental pressure, temperature and reaction starting time, and reduce experimental difficulty and steps of carbon dioxide content measurement and improve measurement accuracy of carbon dioxide content in phosphorite by connecting a pretreatment device and the gas chromatograph.
Description
Technical Field
The invention relates to the technical field of gas content detection, in particular to a method for measuring the carbon dioxide content in phosphorite.
Background
The current national standard GB/T1876-1995 adopts a gas flow method for measuring carbon dioxide in phosphorite, the instrument device involved in the method is huge, one meter long, one meter high, 12 glass containers in the device, 5 cock, more than 2 meters for connecting rubber pipe lines, more than 20 joints, and the phenomenon of gas leakage or liquid leakage can occur slightly carelessly. The standard method comprises solid-liquid reaction, gas collection and gas absorption, wherein in the gas collection part, the gas is collected in a branch gas pipe by utilizing liquid level difference, in order to ensure that the gas pressure is consistent with the laboratory pressure, a balance bottle, a compensation pipe, a lower mouth bottle and the like are arranged in the device, an 800mm laboratory table is taken as a base, and in order to achieve a certain liquid level difference during the exhaust, an operator needs to stand on the laboratory table, so that the operation is time-consuming and labor-consuming.
The literature one (research Dong Defan for measuring carbon dioxide in mineral rock by gas chromatography, volume 17, 1994, gas chromatography, etc.) adopts gas chromatography to measure carbon dioxide content in mineral rock, and has the following disadvantages: a, the volume of the gas is greatly changed under pressure, a dissolved sample gas preparation device adopted in the data can prepare and collect the gas, and the problem of balance of gas pressure can be solved by using a balloon to collect the gas, but because the density of carbon dioxide is high, the generated gas can be deposited in a reaction bottle, and the representativeness of the obtained sample is not strong; the volume of the gas is greatly changed by the temperature, the temperature of the gas is not controlled in the method, and the literature only stipulates that the temperature of the gas is not allowed to exceed 91 ℃ after the gas is sucked, and the content difference of carbon dioxide in the gas with the same volume and different temperatures is large; c, the total volume change of the gas causes the change of the volume fraction of the carbon dioxide in the same volume of the gas, the influence caused by the total volume change is not considered in the literature, the total volume change is calculated by the reaction bottle volume of 50mL and is not negligible, and if the total volume change is ignored, the linear correlation between the peak area and the mass of the carbon dioxide is reduced, namely the curve is deviated; d, the difference of the components of the standard substance (calcium carbonate) and the tested substance (mineral rock) causes the inconsistency of the time and the reaction temperature of complete reaction, and the incomplete reaction of the mineral rock and the like are easy to cause the deviation of analysis results.
In the second literature (metallurgical analysis, determination of carbon dioxide Dan Zhisheng in ore by gas chromatography in the 06 th year 1983, etc.), the following drawbacks are found: a, the volume of the gas is greatly changed by temperature and pressure, the gas expands when heated, and the rubber plug is easily jacked up when the gas expands in water bath at 90 ℃ for three minutes; b, the small-volume sample injector in the literature is only about 5mL, under the sealing condition, the volume is changed into 3.5mL when hydrochloric acid is added, and even if the plug is not opened at the top of the generated carbon dioxide, the volumes of the gases carried into the chromatographic column by the carrier gas are not equal under normal pressure, and the masses are not equal; c, using solid calcium carbonate as a standard substance to make a standard curve, and not considering the problems of temperature, pressure and sample injection volume, and also having the problems in the second document.
From the background, it can be seen that the carbon dioxide of the mineral substance is detected by gas chromatography, and the detected components are required to be converted into gas and loaded into a chromatographic column for separation, namely, the sealing and decomposition reaction conditions play a very important role in the success or failure of the experiment.
Disclosure of Invention
In order to solve the defects that the temperature, the pressure and the reaction starting time are not easy to control, the measuring device is too huge and the operation method is complex in the measuring method in the prior art, the invention provides the method for measuring the carbon dioxide content in the phosphorite, which can accurately control the experimental pressure, the temperature and the reaction starting time, and reduce the experimental difficulty and the steps of measuring the carbon dioxide content by utilizing the pretreatment device and gas chromatography connection, and improve the measuring accuracy of the carbon dioxide content in the phosphorite.
The invention provides a method for measuring the carbon dioxide content in phosphorite, which comprises the following steps:
step 1: setting gas chromatograph conditions, preparing CO with different volume fractions by using standard gas 2 Standard gas, CO production 2 A standard curve;
step 2: adding a phosphorite sample and a phosphoric acid solution into a pretreatment device for reaction, and preparing gas to be detected;
step 3: and collecting the gas to be detected, ensuring the temperature and the pressure of the gas, and recording the total volume V of the obtained gas.
Step 4: injecting the gas to be detected into a sample injector of a gas chromatograph to obtain the volume fraction of carbon dioxide
Step 5: and calculating the content of carbon dioxide in the phosphorite.
As a further improvement of the above scheme, the gas chromatograph conditions are specifically: a thermal conductivity detector (detector temperature 110 ℃, hot wire temperature 150 ℃, bridge flow 156 mV), chromatographic column (TDX-01,column temperature 90 deg.c, injector (six-way valve injection, temperature 90 deg.c), carrier gas (hydrogen).
As a further improvement of the scheme, the pretreatment device comprises a reaction bottle and a support frame, wherein the reaction bottle is arranged on the support frame, a heating mechanism is arranged at the bottom of the reaction bottle, a sample groove is formed in the bottom of the reaction bottle, a cover body is arranged on the side wall of the reaction bottle, a cooling cavity is formed between the cover body and the side wall of the reaction bottle, a water inlet and a water outlet are formed in the cover body, a sealing plug is arranged at the port of the reaction bottle, a thermometer is arranged on the sealing plug, a temperature measuring end of the thermometer stretches into the reaction bottle, a first glass tube and a second glass tube are arranged on the sealing plug, one end of the first glass tube is communicated with the reaction bottle, the other end of the first glass tube is connected with a first piston measuring cylinder through a connecting hose, one end of the second glass tube is communicated with the reaction bottle, a three-way valve with a cock is connected to the other end of the second glass tube, a first port of the three-way valve is connected with the second glass tube through the connecting hose, and a third port of the three-way valve can be connected with a sampling device of a gas chromatograph.
As the further improvement of above-mentioned scheme, the support frame is including the base, be equipped with two guide bars on the base, two the cover is equipped with the sliding block on the guide bar, the sliding block lateral part is equipped with first fixing bolt, the sliding block middle part sets up the level and perforates, the level is perforated the cover and is equipped with the dead lever, sliding block upper portion is equipped with the second fixing bolt, the dead lever tip is equipped with places the ring, the reaction bottle is placed in and is placed on the ring, place and be equipped with a plurality of spacing spout on the ring, be equipped with spacing slide bar in the spacing spout, the cover is equipped with spacing separation blade and spacing spring on the spacing slide bar, spacing spring one end is connected with spacing spout, and the other end is connected with the side of spacing separation blade.
As the further improvement of above-mentioned scheme, first piston graduated flask and second piston graduated flask all set up on the crane, the crane is including the base, be provided with two guide posts on the base, sliding connection has the elevating platform on the guide post, be equipped with adjusting spring between elevating platform and the base, the lower part of elevating platform is provided with the holding ring, be equipped with first locating hole on the holding ring, be provided with a plurality of second locating holes on the guide post, correspond first locating hole and second locating hole are equipped with the locating pin, the elevating platform lateral part is equipped with the handle.
As a further improvement of the above scheme, the heating mechanism may be an alcohol lamp or an electric stove.
As a further improvement of the scheme, the bottom of the reaction bottle is of a single-layer silicon boron glass structure, the lower pipe orifice of the first glass pipe extends out of the bottom of the sealing plug, and the lower pipe orifice of the second glass pipe is flush with the bottom of the sealing plug.
As a further improvement of the above scheme, the volume of the reaction bottle is 50mL, and the volume of the sample tank is 2.5mL.
As a further improvement of the above scheme, the preparation steps of the detection gas in the step 2 are as follows: 0.1-0.5g of phosphorite sample is weighed to be accurate to 0.1mg in a sample groove in a reaction bottle, and 10-15mL of 1+1 phosphoric acid solution is accurately removed outside the sample groove; extracting 40mL of air in the first piston measuring cylinder and the second piston measuring cylinder, connecting a sealing plug and a reaction bottle, mixing a phosphorite sample with a phosphoric acid solution, and heating; when the temperature rises to 80 ℃, keeping the solution in a micro-boiling state, and keeping the temperature at 80 ℃ for two minutes; stopping heating and introducing cooling water into the cover body to cool until the display value of the thermometer is the same as the room temperature; pushing the first piston measuring cylinder and the second piston measuring cylinder to uniformly mix the gases in the reaction bottle and the connecting pipeline to obtain the gas to be detected; pushing the first piston measuring cylinder to clear the volume of gas in the first piston measuring cylinder, pulling the piston of the second piston measuring cylinder, extracting the gas to be detected, and after the piston is automatically balanced, rotating the cock of the three-way valve to only keep the sampler communicated with the second piston measuring cylinder, pushing the piston of the second piston measuring cylinder, and injecting the gas to be detected into the sampler of the gas chromatograph.
As a further improvement of the scheme, the specific steps of the content of carbon dioxide in the phosphorite in the step 4 are as follows: the total volume of gas V, v=v, is obtained first 1 +V 3 -V 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein V is 1 V is the total volume of the reaction bottle and the connecting pipeline 2 The dropping volume of the phosphoric acid solution is; v (V) 3 To only keep the volume of the gas to be detected in the second piston measuring cylinder when the sampler is communicated with the second piston measuring cylinder; calculating the content of carbon dioxide in phosphorite by a formula:
wherein the method comprises the steps of-the volume fraction,%;
v-total volume of gas, mL;
m-mass of phosphorite sample, g;
f, calculating a correction coefficient F when converting gas into standard conditions according to the laboratory environment temperature and the atmospheric pressure:
p-laboratory atmospheric pressure, kPa;
P w -partial pressure of gas and steam at t ℃ kPa;
t-laboratory temperature, DEG C;
8.314-gas constant, J/mol.K;
44.00-molar mass of carbon dioxide, g/mol.
The beneficial effects of the invention are as follows:
compared with the prior art, the method for measuring the carbon dioxide content in the phosphorite can realize monitoring of the reaction starting time, the reaction temperature and the reaction speed of reactants in the reaction bottle by utilizing the cooperation of the heating mechanism and the thermometer, and realizes rapid cooling of gas by injecting circulating cooling water into a cooling cavity formed by the reaction bottle and the cover body; the pressure balance problem of the gas caused by temperature can be solved by utilizing the first piston measuring cylinder and the second piston measuring cylinder, in addition, the generated gas can be uniformly mixed by mutually pushing the first piston measuring cylinder and the second piston measuring cylinder, and the communication between the second piston measuring cylinder and a sampler of a gas chromatograph can be realized by utilizing the three-way valve; the placing height of the reaction bottle can be adjusted by utilizing the supporting frame according to the requirements of operators; the height of the first piston measuring cylinder and the second piston measuring cylinder can be adjusted by utilizing the lifting frame, so that the smooth flow of gas in the connecting hose is ensured; the method for measuring the carbon dioxide content in the phosphorite can accurately control the experimental pressure, the temperature and the reaction starting time, and reduces the experimental difficulty and the steps of carbon dioxide content measurement by utilizing the pretreatment device to connect with the gas chromatograph, thereby improving the measurement accuracy of the carbon dioxide content in the phosphorite.
Drawings
FIG. 1 is a schematic diagram of the present invention;
FIG. 2 is a schematic diagram of a pretreatment device according to the present invention;
FIG. 3 is a schematic view of a supporting frame according to the present invention;
FIG. 4 is a schematic view of a structure of a lifting frame according to the present invention;
FIG. 5 is a schematic view of a lifting platform according to the present invention;
FIG. 6 is a schematic structural view of a reaction flask according to the present invention;
fig. 7 is a schematic view of the structure of the sealing plug of the present invention.
In the figure: reaction flask 1, cover 101, sample tank 102, support frame 2, base 201, guide bar 202, slider 203, first fixing bolt 204, fixing bar 205, second fixing bolt 206, placement ring 207, limit chute 208, limit slide bar 209, limit stopper 2010, limit spring 2011, heating mechanism 3, sealing plug 4, first glass tube 5, second glass tube 6, first piston cylinder 7, three-way valve 8, second piston cylinder 9, lifting frame 10, base 1001, guide column 1002, lifting table 1003, adjusting spring 1004, positioning ring 1005, first positioning hole 1006, second positioning hole 1007, positioning pin 1008, handle 1009, thermometer 11.
Detailed Description
Example 1
The invention provides a method for measuring the carbon dioxide content in phosphorite, which comprises the following steps:
step 1: setting gas chromatograph conditions, specifically: the temperature of the detector of the thermal conductivity detector is 110 ℃, the temperature of the hot wire is 150 ℃, the bridge flow is 156mV, the chromatographic column TDX-01,the column temperature is 90 ℃, the sample is injected by a six-way valve of a sample injector, the temperature is 90 ℃, and the carrier gas is hydrogen, and CO with different volume fractions is prepared by standard gas 2 Standard gas, CO production 2 A standard curve.
Step 2: the method comprises the steps of controlling reaction conditions, adding a phosphorite sample and a phosphoric acid solution into a pretreatment device for reaction to prepare gas to be detected, wherein the pretreatment device comprises a reaction bottle 1 and a support frame 2, the reaction bottle 1 is arranged on the support frame 2, a heating mechanism 3 is arranged at the bottom of the reaction bottle 1, a sample groove 102 is arranged in the bottom of the reaction bottle 1, a cover body 101 is arranged on the side wall of the reaction bottle 1, a cooling cavity is formed by the cover body 101 and the side wall of the reaction bottle 1, a water inlet and a water outlet are arranged on the cover body 101, a sealing plug 4 is arranged at a port of the reaction bottle 1, a thermometer 11 is arranged on the sealing plug 4, a temperature measuring end of the thermometer 11 stretches into the reaction bottle 1, the temperature of the gas to be detected is monitored and controlled, a first glass tube 5 and a second glass tube 6 are arranged on the sealing plug 4, one end of the first glass tube 5 is communicated with the reaction bottle 1, a first piston measuring cylinder 7 is connected to the other end of the first glass tube 5 through a connecting hose, one end of the second glass tube 6 is communicated with the reaction bottle 1, a three-way valve 8 with the other end of the reaction bottle 1 through a cock, a three-way valve 8 is connected to the second port of the three-way valve 8 through a third port of the three-way valve 8, and a gas chromatograph is connected to a third port of a gas chromatograph through a connecting port 9;
the volume of the piston measuring cylinder and the volume of the reaction bottle 1 are mutually influenced, the volume of the piston measuring cylinder is about twice the volume of the reaction bottle, the volume of air to be extracted before reaction is about 40% of the volume of the piston measuring cylinder, if a certain amount of gas is not extracted in advance, the generated carbon dioxide is easy to gather at the bottom of the reaction bottle 1 and cannot be uniformly mixed, the extraction volume is too small, the gas cannot be fully mixed, and if the extraction volume is too large, the gas is easy to cause the falling of a piston rod during mixing, so that the volume of the extracted gas is determined to be basically the same as the actual volume of the reaction bottle 1, the design principle of the reaction bottle 1 is small and good, the reaction is facilitated, and the whole device is enlarged due to the excessively large volume and is inconvenient to operate; when the volume is too small, the gas amount is too small, the displacement amount is small when the gas enters the chromatograph, and the displacement of the quantitative tube is not clean;
the support frame 2 comprises a base 201, two guide rods 202 are arranged on the base 201, sliding blocks 203 are sleeved on the two guide rods 202, first fixing bolts 204 are arranged on the side parts of the sliding blocks 203, horizontal through holes are formed in the middle parts of the sliding blocks 203, fixing rods 205 are sleeved on the horizontal through holes, second fixing bolts 206 are arranged on the upper parts of the sliding blocks 203, a placing ring 207 is arranged at the end parts of the fixing rods 205, reaction bottles 1 are placed on the placing ring 207, a plurality of limiting sliding grooves 208 are arranged on the placing ring 207, limiting sliding rods 209 are arranged in the limiting sliding grooves 208, limiting baffle plates 2010 and limiting springs 2011 are sleeved on the limiting sliding rods 209, one ends of the limiting springs 2011 are connected with the limiting sliding grooves 208, and the other ends of the limiting springs are connected with the side surfaces of the limiting baffle plates 2010;
the first piston measuring cylinder 7 and the second piston measuring cylinder 9 are both arranged on the lifting frame 10, the lifting frame 10 comprises a base 1001, two guide posts 1002 are arranged on the base 1001, a lifting table 1003 is connected to the guide posts 1002 in a sliding manner, an adjusting spring 1004 is arranged between the lifting table 1003 and the base 1001, a positioning ring 1005 is arranged at the lower part of the lifting table 1003, a first positioning hole 1006 is arranged on the positioning ring 1005, a plurality of second positioning holes 1007 are arranged on the guide posts 1002, positioning pins 1008 are arranged corresponding to the first positioning holes 1006 and the second positioning holes 1007, and handles 1009 are arranged on the side parts of the lifting table 1003;
the heating mechanism 3 can be an alcohol lamp or an electric furnace; the bottom of the reaction bottle 1 is of a single-layer silicon boron glass structure, the lower pipe orifice of the first glass pipe 5 extends out of the bottom of the sealing plug 4, and the lower pipe orifice of the second glass pipe 6 is flush with the bottom of the sealing plug 4;
the volume of the reaction bottle 1 is 50mL, the volume of the sample tank 102 is 2.5mL, the size of the sample tank 102 determines the adding amount of phosphoric acid, the phosphoric acid is suitable for filling phosphorite by a medicine spoon, the adding amount of the acid is related to the height of the sample tank 102, if the height of the sample tank 102 is lower, the adding amount of the phosphoric acid can be less, if the height of the sample tank 102 is higher, the adding amount of the phosphoric acid needs more, and in principle, the full mixing of the phosphorite and the phosphoric acid during shaking is ensured;
the preparation steps of the detection gas are as follows: controlling reaction conditions, weighing 0.1035g of phosphorite sample into the sample tank 101, and transferring 10mL of 1+1 phosphoric acid solution out of the sample tank 101; extracting 40mL of air in the first piston measuring cylinder 7 and the second piston measuring cylinder 9 in advance, connecting a sealing plug and a reaction bottle, mixing a phosphorite sample with a phosphoric acid solution, and heating; when the temperature rises to 80 ℃, keeping the solution in a micro-boiling state, and keeping the temperature at 80 ℃ for two minutes; stopping heating and introducing cooling water into the cover body 101 to cool until the display value of the thermometer 11 is the same as the room temperature; pushing the first piston measuring cylinder 7 and the second piston measuring cylinder 9 to uniformly mix the gases in the reaction bottle 1 and the connecting pipeline to obtain the gas to be detected; pushing the first piston measuring cylinder 7 to clear the volume of gas in the first piston measuring cylinder, pulling the piston of the second piston measuring cylinder 9, rotating the cock of the three-way valve 8 to only keep the communication between the sampler and the second piston measuring cylinder 9 after the piston is automatically balanced, pushing the piston of the second piston measuring cylinder 9, and injecting the gas to be detected into the sampler of the gas chromatograph;
step 3: collecting the gas to be detected, ensuring the temperature and pressure of the gas, and recording the total volume V of the obtained gas, wherein V=V 1 +V 3 -V 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein V is 1 Is the total volume of the reaction bottle and the connecting pipeline，V 2 The dropping volume of the phosphoric acid solution is; v (V) 3 To maintain only the volume of gas to be detected in the second piston cylinder when the sampler and the second piston cylinder are in communication, the total volume of gas v=51.0+90.0-10.0= 131.0mL.
Step 4: injecting the gas to be detected into a sample injector of a gas chromatograph to obtain the volume fraction of carbon dioxide
Step 5: calculating the content of carbon dioxide in phosphorite, and passing through the formula:
calculating the content CO of carbon dioxide in phosphorite 2 ％＝17.18％。
Example 2
Compared with embodiment 1, this embodiment differs in that: weighing 0.2068g of phosphorite sample, and transferring 15mL of 1+1 phosphoric acid solution out of the sample tank 101; total volume of gas obtained v=51.0+83.0-15.0=119.0 mL; volume fraction of carbon dioxide obtainedContent of carbon dioxide CO in phosphorite 2 ％＝3.41％。
Example 3
Compared with example 1, the difference of this example is that 0.3151g of phosphorite sample is weighed and 10mL of 1+1 phosphoric acid solution is removed outside the sample tank 101; total volume of gas obtained v=51.0+84.0-10.0=125.0 mL; volume fraction of carbon dioxide obtainedContent of carbon dioxide CO in phosphorite 2 ％＝4.17％。
Example 4
Compared with example 1, the difference of this example is that 0.4173g of phosphorite sample is weighed and 15mL of 1+1 phosphoric acid solution is removedThe sample tank 101 is outside; total volume of gas obtained v=51.0+86.0-15.0=122.0 mL; volume fraction of carbon dioxide obtainedContent of carbon dioxide CO in phosphorite 2 ％＝3.73％。
Example 5
Compared with example 1, the difference of this example is that 0.5022g of phosphorite sample is weighed, and 15mL of 1+1 phosphoric acid solution is removed outside the sample tank 101; total volume of gas obtained v=51.0+91.0-15.0=127.0 mL; volume fraction of carbon dioxide obtainedContent of carbon dioxide CO in phosphorite 2 ％＝0.81％。
Example 6
Compared with example 1, the difference of this example is that the reference calcium carbonate 0.1008 is weighed and 15mL of 1+1 phosphoric acid solution is removed from the sample tank 101; total volume of gas obtained v=51.0+92.0-15.0=128.0 mL; volume fraction of carbon dioxide obtainedContent of carbon dioxide CO in phosphorite 2 ％＝44.02％。
In the experiment, the sample weighing amount of phosphorite can be in a certain range, the sample weighing amount can be less when the content of carbon dioxide is high, the sample weighing amount can be more when the content of carbon dioxide is low, the sample weighing amount is related to the highest point of a standard curve in the chromatograph, the standard curve is manufactured by gradually diluting the sample in the embodiment 6 with the concentration of 25.9 percent of carbon dioxide, and the sample weighing amount is not required to be less than 0.1g because the sample in the embodiment 6 is the standard calcium carbonate and the carbon dioxide in the phosphorite generally does not exceed the content of the carbon dioxide in the calcium carbonate.
Precision and accuracy test data:
in the test, the reference is adopted respectivelyCalcium carbonate and two standard substances of phosphorite are used as standards, 10 groups of data are measured on each standard substance by the measuring method in the invention, and the CO of the three standard substances can be seen from the table 2 Determination of the average value and the CO of the corresponding standard substance 2 The standard value has small error and the variation coefficient of the three is between 0.12 and 2.32 percent, which proves that the method has higher measurement precision, and the confidence coefficient t value of the three is less than t when the confidence coefficient t value of the three is less than 95 percent 0.05,10 (t 0.05,10 =2.228), which indicates that the measurement accuracy of the method is higher.
The above embodiments are not limited to the technical solution of the embodiments, and the embodiments may be combined with each other to form a new embodiment. The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and any modifications or equivalent substitutions without departing from the spirit and scope of the present invention should be covered in the scope of the technical solution of the present invention.
Claims (8)
1. A method for measuring the carbon dioxide content in phosphorite is characterized in that: the method comprises the following steps:
step 1: setting gas chromatograph conditions, preparing CO with different volume fractions by using standard gas 2 Standard gas, CO production 2 A standard curve;
step 2: adding a phosphorite sample and a phosphoric acid solution into a pretreatment device for reaction, and preparing gas to be detected; the pretreatment device comprises a reaction bottle (1) and a support frame (2), the reaction bottle (1) is arranged on the support frame (2), a heating mechanism (3) is arranged at the bottom of the reaction bottle (1), a sample groove (102) is arranged in the bottom of the reaction bottle (1), a cover body (101) is arranged on the side wall of the reaction bottle (1), a cooling cavity is formed by the cover body (101) and the side wall of the reaction bottle (1), a water inlet and a water outlet are arranged on the cover body (101), a sealing plug (4) is arranged at the port of the reaction bottle (1), a thermometer (11) is arranged on the sealing plug (4), the temperature measuring end of the thermometer (11) stretches into the reaction bottle (1), a first glass tube (5) and a second glass tube (6) are arranged on the sealing plug (4), one end of the first glass tube (5) is communicated with the reaction bottle (1), the other end of the first glass tube (5) is connected with a first piston measuring cylinder (7) through a connecting hose, one end of the second glass tube (6) is communicated with the reaction bottle (1) through a cock (8), the other end of the second glass tube (6) is connected with a third valve (8), a second port of the three-way valve (8) is connected with a second piston measuring cylinder (9) through a connecting hose, and a third port of the three-way valve (8) can be connected with a sampler of a gas chromatograph; the preparation steps of the gas to be detected are as follows: 0.1-0.5g of phosphorite sample is accurately weighed to 0.1mg in a sample tank 101 of the reaction bottle 1, and 10-15mL of 1+1 phosphoric acid solution is accurately removed outside the sample tank 101; mixing a phosphorite sample with a phosphoric acid solution and heating; when the temperature rises to 80 ℃, keeping the solution in a micro-boiling state, and keeping the temperature at 80 ℃ for two minutes; stopping heating and introducing cooling water into the cover body (101) to cool until the display value of the thermometer (11) is the same as the room temperature; 40mL of air is extracted in the first piston measuring cylinder (7) and the second piston measuring cylinder (9) in advance, and the first piston measuring cylinder (7) and the second piston measuring cylinder (9) are pushed to ensure that the gases in the reaction bottle (1) and the pipeline are uniformly mixed, so as to obtain the gas to be detected; pushing the first piston measuring cylinder (7) to clear the volume of gas in the cylinder, pulling the piston of the second piston measuring cylinder (9), extracting the gas to be detected, and after the piston is automatically balanced, rotating the cock of the three-way valve (8) to only keep the sampler communicated with the second piston measuring cylinder (9), pushing the piston of the second piston measuring cylinder (9), and injecting the gas to be detected into the sampler of the gas chromatograph;
step 3: injecting the gas to be detected into a sample injector of a gas chromatograph to obtain the volume fraction of carbon dioxide
Step 4: and calculating the content of carbon dioxide in the phosphorite.
2. A method for determining the carbon dioxide content of phosphate rock according to claim 1, characterized in that: the gas chromatograph conditions are specifically as follows: thermal conductivity detector: detector temperature 110 ℃, hot wire temperature 150 ℃, bridge flow 156mV; chromatographic column: the total number of the components of the TDX-01,column temperature 90 ℃; sample injector: sampling by a six-way valve, wherein the temperature is 90 ℃; carrier gas: hydrogen gas.
3. A method for determining the carbon dioxide content of phosphate rock according to claim 1, characterized in that: the heating mechanism (3) is an alcohol lamp or an electric stove.
4. A method for determining the carbon dioxide content of phosphate rock according to claim 1, characterized in that: the bottom of the reaction bottle (1) is of a single-layer silicon boron glass structure.
5. A method for determining the carbon dioxide content of phosphate rock according to claim 1, characterized in that: support frame (2) is including base (201), be equipped with two guide bars (202) on base (201), two cover is equipped with slider (203) on guide bar (202), slider (203) lateral part is equipped with first fixing bolt (204), slider (203) middle part sets up horizontal perforation, horizontal perforation cover is equipped with dead lever (205), slider (203) upper portion is equipped with second fixing bolt (206), dead lever (205) tip is equipped with places ring (207), place ring (207) are placed in reaction bottle (1), place and be equipped with a plurality of spacing spout (208) on ring (207), be equipped with spacing slide bar (209) in spacing slide bar (208), the cover is equipped with spacing separation blade (2010) and spacing spring (2011) on spacing slide bar (209), spacing spring (2011) one end is connected with spacing spout (208), and the other end is connected with the side of spacing separation blade (2010).
6. A method for determining carbon dioxide content in phosphorite according to claim 5, characterized in that: the lifting device comprises a lifting frame (10) and is characterized in that a first piston measuring cylinder (7) and a second piston measuring cylinder (9) are arranged, the lifting frame (10) comprises a base (1001), at least two guide columns (1002) are arranged on the base (1001), lifting platforms (1003) are slidably connected to the guide columns (1002), adjusting springs (1004) are arranged between the lifting platforms (1003) and the base (1001), positioning rings (1005) are arranged on the lower portions of the lifting platforms (1003), first positioning holes (1006) are formed in the positioning rings (1005), a plurality of second positioning holes (1007) are formed in the guide rods (202), positioning pins (1008) are arranged in the corresponding first positioning holes (1006) and the second positioning holes (1007), and handles (1009) are arranged on the side portions of the lifting platforms (1003).
7. A method for determining the carbon dioxide content of phosphate rock according to claim 1, wherein: the volume of the reaction bottle (1) is 50mL, and the volume of the sample tank (102) is 2.5mL.
8. A method for determining the carbon dioxide content of phosphate rock according to claim 1, characterized in that: the specific steps of the content of carbon dioxide in the phosphorite in the step 4 are as follows: the total volume of gas V, v=v, is obtained first 1 +V 3 -V 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein V is 1 V is the total volume of the reaction bottle and the connecting pipeline 2 The dropping volume of the phosphoric acid solution is; v (V) 3 To keep the volume of gas to be detected in the second piston cylinder (9) only when the sampler is in communication with the second piston cylinder (9); calculating the content of carbon dioxide in phosphorite by a formula:
wherein the method comprises the steps of-the volume fraction,%;
v-total volume of gas, mL;
m-mass of phosphorite sample, g
F, calculating a correction coefficient F when converting gas into standard conditions according to the laboratory environment temperature and the atmospheric pressure:
p-laboratory atmospheric pressure, kPa;
P w -partial pressure of gas and steam at t ℃ kPa;
t-laboratory temperature, DEG C;
8.314-gas constant, J/mol.K;
44.00-molar mass of carbon dioxide, g/mol.
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